Inter­molecular C—H...O and C—H...X inter­actions in substituted spiro­acenaphthylene structures

In the three spiro­acenaphthylene structures 5′′-[(E)-2,3-dichloro­benzyl­idene]-7′-(2,3-dichloro­phenyl)-1′′-methyldispiro­[ace­naphthyl­ene-1,5′-pyrrolo­[1,2-c][1,3]thia­zole-6′,3′′-piperidine]-2,4′′-dione, C₃₅H₂₆Cl₄N₂O₂S, (I), 5′′-[(E)-4-fluoro­benzyl­idene]-7′-(4-fluoro­phenyl)-1′′-methyldispiro­[acenaphthyl­ene-1,5′-pyrrolo­[1,2-c][1,3]thia­zole-6′,3′′-piperidine]-2,4′′-dione, C₃₅H₂₈F₂N₂O₂S, (II), and 5′′-[(E)-4-bromo­benzylidene]-7′-(4-bromo­phenyl)-1′′-methyldispiro­[ace­naphthylene-1,5′-pyrrolo­[1,2-c][1,3]thia­zole-6′,3′′-piperidine]-2,4′′-dione, C₃₅H₂₈Br₂N₂O₂S, (III), the substituted aryl groups are 2,3-dichloro-, 4-fluoro- and 4-bromo­phenyl, respectively. The six-membered piperidine ring in all three structures adopts a half-chair conformation, the thia­zolidine ring adopts a slightly twisted envelope and the pyrrolidine ring an envelope conformation; in each case, the C atom linking the rings is the flap atom. In all three structures, weak intra­molecular C—H...O inter­actions are present. The crystal packing is stabilized through a number of inter­molecular C—H...O and C—H...X inter­actions, where X = Cl in (I) and F or S in (II), and C—H...O inter­actions are observed predominantly in (III). In all three structures, mol­ecules are linked through centrosymmetric ring motifs, further tailored through a relay of C—H...X [Cl in (I), Br in (II) and O in (III)] inter­actions.

S1. Comment

The piperidine ring is a distinct structural feature in a variety of alkaloid natural products and drug candidates. During the past decade, thousands of piperidine compounds have been reported in clinical and preclinical studies (Watson et al., 2000). Piperidinones, though less prominent, are also precursors to a host of biologically active compounds and natural alkaloids, prior to their conversion to piperidines. Spiro systems are also of interest as they exhibit a wide range of biological activities (Kobayashi et al., 1991; James et al., 1991). Spiropyrrolidines have attracted much attention as potential antileukaemic and anticonvulsant agents (Abou Gharbia et al., 1979), with antiviral (Lundahl et al., 1972) and local anaesthetic (Kornett & Thio, 1976) activities. Our interest in preparing pharmacologically active piperidones led us to the title compounds, (I)–(III), and especially the study of their conformational features. There are few structures in the Cambridge Structral Database (CSD, Version?; Allen, 2002) containing pyrrrolothiazine ring systems and this is the first report with the attached five-membered ring. Hence, these structures are presumed to be interesting and contain rarely studied moieties.

The six-membered piperidine rings in all three compounds (Figs. 1–3) adopt the half-chair conformation, with deviations of atoms N1 and C5 from the least-squares plane defined by atoms C2/C3/C4/C6 of 0.613 (3) and 0.509 (3) Å in (I), 0.553 (3) and 0.562 (3) Å in (II), and 0.545 (3) and 0.565 (3) Å in (III), respectively. The differences in the deviations are due to steric hindrance of the different substituents at the C3 and C5 positions of the piperidine ring. The olefinic double bond in all three structures has an E conformation and the pyrrolidine ring is in an envelope conformation. The thiazolidine ring is in a twisted envelope conformation with atom C8 at the flap, with a pseudo-twofold axis passing through atom S1 and the C8—N2 bond. The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) are q₂ = 0.356 (2) Å, ϕ = -78.0 (4)° and Δs(C8) = 0.035 (1) Å for the thiazolidine ring, and q₂ = 0.263 (2) Å, ϕ = -178.2 (4)° and Δs(C8) = 0.010 (1) Å for the pyrrolidine ring of (I); q₂ = 0.419 (2) Å, ϕ = -93.3 (3)° and Δs(S1) = 0.016 (1) Å for the thiazolidine ring, and q₂ = 0.456 (2) Å, ϕ = -0.4 (3)° and Δs(C8) = 0.001 (1) Å for the pyrrole [pyrrolidine?] ring of (II); and q₂ = 0.440 (3) Å, ϕ = -75.0 (4)° and Δs(C8) = 0.029 (1) Å for the thiazolidine ring, and q₂ = 0.460 (3) Å, ϕ = 144.6 (4)° and Δs(C8) = 0.011 (1) Å for the pyrrolidine ring of (III).

The aryl rings in all three structures are not coplanar with the mean plane of the piperidone ring; the torsion angle C3—C31—C32—C37 is 32.4 (3)° in (I), 9.6 (4)° in (II) and 43.7 (5)° in (III). This lack of coplanarity is caused by nonbonded interactions between one of the ortho H atoms in the aryl ring and the equatorial H atoms at the 2-position of the piperidone ring (H37/H2A or H2B). Steric repulsions are reduced by the expansion of the C3—C31—C32 angle [129.57 (19)° in (I), 132.7 (2)° in (II) and 127.1 (3)° in (III)]. The dihedral angle between the dichlorophenyl rings is 58.4 (1)° in (I), that between the fluorophenyl rings is 87.2 (1)° in (II), and that between the bromophenyl rings is 86.1 (1)° in (III), and these rings make angles of 56.5 (1) and 65.2 (1)° in (I), 45.4 (1) and 43.1 (1)° in (II), and 48.7 (1) and 48.4 (1)° in (III) with their respective acenaphthene group.

The C—C distances in the acenaphthene group range from 1.354 (3) (C21—C22) to 1.588 (2) Å (C11—C12) in (I), from 1.360 (2) (C21—C22) to 1.571 Å (C11—C12) in (II) and from 1.350 (C21—C22) to 1.565 Å (C11—C12) in (III), and the C—C—C angles are in the ranges 101.01 (16)–124.1 (2)° in (I), 101.93 (16)–123.1 (2)° in (II) and 101.3 (2)–123.6 (3)° in (III). These compare with those of related structures (Hazell, 1976; Hazell & Hazell, 1977; Hazell & Weigelt, 1976; Jones et al. 1992; Sundar et al., 2002). The C8—N2 bond length is 1.451 (3) Å in (I), 1.448 (4) Å in (II) and 1.454 (3) Å in (III) and these values are comparable with the Csp²—Nsp² distances found in similar structures (Sussman & Wodak, 1973; Wodak, 1975). All three title structures feature a weak intramolecular C—H···O interaction.

In all three structures, due to the lack of suitable donor and acceptor atoms for classical hydrogen bonding, the crystal structures are stabilized through intermolecular C—H···X interactions [X = Cl in (I), F in (II) and O in (III)]. These C—H···X interactions lead to primary ring motifs around inversion centres, which are further connected through chain motifs (Bernstein et al., 1995).

In (I), the molecules are connected through a C2B—H2B···Cl1ⁱⁱ interaction, leading to an R₂²(16) ring around the inversion centres of the unit cell (Fig. 4) and this ring, translated by a unit cell along the b axis connected by an intermolecular C74—H74···Cl1ⁱ interaction (see Table 1 for symmetry codes), leads to a C(14) chain extending along the b axis (Fig. 5). These chains or rings do not have linking C—H···O or C—H···π interactions.

In (II), one C73—H73···O2ⁱⁱⁱ and two C37—H37···F2ⁱⁱ interactions lead to an unusual R₃³(27) ring (Fig. 6), which is connected through a secondary C₂²(14) chain extending along the ab diagonal of the unit cell (Fig. 7), formed through C37—H37···F2ⁱⁱ and C33—H33···S1ⁱ interactions (see Table 2 for symmetry codes).

In (III), all the intermolecular interactions are of the C—H···O type (Table 3). The crystal packing features two dimeric R₂²(16) and R₂²(14)R₂²(16) ring motifs formed through C73—H73···O1ⁱⁱⁱ and C76—H76···O2ⁱⁱ/C9—H9A···O2ⁱⁱ hydrogen bonds (Fig. 8 and 9). These C—H···O dimers are arranged in tandem and form a zigzag C(8) chain extending along the b axis through a C34—H34···O1ⁱ interaction (Fig. 10) (see Table 3 for symmetry codes).

Thus, all three title spiroacenaphthene crystal structures are stabilized through nonclassical C—H···X interactions with primary ring and secondary chain motifs.

Related literature

For related literature, see: Abou & Doukas (1979); Allen (2002); Bernstein et al. (1995); Cremer & Pople (1975); Hazell (1976); Hazell & Hazell (1977); Hazell & Weigelt (1976); James et al. (1991); Jones et al. (1992); Kobayashi et al. (1991); Kornett & Thio (1976); Lundahl et al. (1972); Nardelli (1983); Sundar et al. (2002); Sussman & Wodak (1973); Watson et al. (2000); Wodak (1975).

S2. Experimental

For the preparation of (I), a mixture of 1-methyl-3,5-bis[(E)-2,3-dichlorobenzylidene]tetrahydropyridin-4(1H)-one (1 mmol), acenaphthenequinone (0.182 g, 1 mmol) and 1,3-thiazolane-4-carboxylic acid (0.133 g, 1 mmol) was dissolved in methanol (10 ml) and refluxed for 30 min. After completion of the reaction as evident from thin-layer chromatography (TLC), the mixture was poured into water (50 ml), and the precipitated solid was filtered off and washed with water (100 ml) to obtain the pure product as a pale-yellow solid. The product was recrystallized from ethyl acetate to obtain suitable crystals of (I) for X-ray analysis (yield 92%, m.p. 477 K).

For the preparation of (II), a mixture of 1-methyl-3,5-bis[(E)-4-flurobenzylidene]tetrahydropyridin-4(1H)-one (1 mmol), acenaphthenequinone (0.182 g, 1 mmol) and 1,3-thiazolane-4-carboxylic acid (0.133 g, 1 mmol) was dissolved in methanol (10 ml) and refluxed for 30 min. After completion of the reaction as evident from TLC, the mixture was poured into water (50 ml), and the precipitated solid was filtered off and washed with water (100 ml) to obtain the pure product as a pale-yellow solid. The product was recrystallized from ethyl acetate to obtain suitable crystals of (II) for X-ray analysis (yield 91%, m.p. 483 K).

For the preparation of (III), a mixture of 1-methyl-3,5-bis[(E)-4-bromobenzylidene]tetrahydropyridin-4(1H)-one (1 mmol), acenaphthenequinone (0.182 g, 1 mmol) and 1,3-thiazolane-4-carboxylic acid (0.133 g, 1 mmol) was dissolved in methanol (10 ml) and refluxed for 30 min. After completion of the reaction as evident from TLC, the mixture was poured into water (50 ml), and the precipitated solid was filtered off and washed with water (100 ml) to obtain the pure product as a pale-yellow solid. The product was recrystallized from ethyl acetate to obtain suitable crystals of (III) for X-ray analysis (yield 91%, m.p. 485 K).

S3. Refinement

H atoms were placed at calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq(C) for CH₂ and CH groups or 1.5U_eq(C) for methyl H atoms.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The molecular structure of (II), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 3. The molecular structure of (III), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 4. A partial packing view for (I), showing the R2^2(16) ring. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 1 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat labels]
	Fig. 5. A partial packing view for (I), showing the C2^2(14) chain extending along the b axis of the unit cell. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 1 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat label]
	Fig. 6. A partial packing view for (II), showing the unusal ring R3^3(27) motif. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 2 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat labels]
	Fig. 7. A partial packing view for (II), showing the C2^2(14) chain extending along the ab diagonal of the unit cell. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 2 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat labels]
	Fig. 8. A partial packing view for (III), showing the R2^2(16) ring. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 3 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat label]
	Fig. 9. A partial packing view for (III), showing the R2^2(14)R2^2(16) ring. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 3 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat labels]
	Fig. 10. A partial packing view for (III), showing the C(8) chain extending along the b axis of the unit cell. Dashed lines indicate hydrogen bonds. Some H atoms have been omitted for clarity. (See Table 3 for symmetry code of acceptor atom.) [Please supply symmetry-code descriptor for repeat label]

(I) 5''-[(E)-2,3-Dichlorobenzylidene]-7'-(2,3-dichlorophenyl)-1''-methyl- dispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''- piperidine]-2,4''-dione

Crystal data

C35H26Cl4N2O2S	F(000) = 1400
Mr = 680.44	Dx = 1.446 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2000 reflections
a = 13.4722 (6) Å	θ = 2–31°
b = 16.4269 (8) Å	µ = 0.48 mm^−1
c = 14.8673 (7) Å	T = 293 K
β = 108.243 (2)°	Block, colourless
V = 3124.9 (3) Å^3	0.19 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker Kappa APEXII area-detector diffractometer	8258 independent reflections
Radiation source: fine-focus sealed tube	5375 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 0 pixels mm^-1	θmax = 29.0°, θmin = 2.0°
ω and ϕ scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −22→20
Tmin = 0.912, Tmax = 0.948	l = −20→20
37631 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0552P)^2 + 1.3138P] where P = (Fo^2 + 2Fc^2)/3
8258 reflections	(Δ/σ)max < 0.001
397 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

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

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
C1	0.5172 (2)	0.11908 (15)	−0.00355 (17)	0.0574 (6)
H1A	0.5591	0.1583	−0.0231	0.086*
H1B	0.4591	0.1034	−0.0570	0.086*
H1C	0.5588	0.0720	0.0218	0.086*
C2	0.42248 (17)	0.23033 (12)	0.03535 (14)	0.0435 (5)
H2A	0.3667	0.2196	−0.0230	0.052*
H2B	0.4699	0.2691	0.0214	0.052*
C3	0.37677 (14)	0.26727 (12)	0.10607 (13)	0.0369 (4)
C4	0.35543 (15)	0.21336 (12)	0.17961 (13)	0.0389 (4)
C5	0.41051 (15)	0.13015 (11)	0.19827 (13)	0.0365 (4)
C6	0.41435 (16)	0.09889 (12)	0.10223 (13)	0.0396 (4)
H6A	0.4442	0.0446	0.1090	0.048*
H6B	0.3444	0.0966	0.0573	0.048*
C7	0.35098 (16)	0.07197 (12)	0.24762 (14)	0.0405 (4)
H7	0.2840	0.0974	0.2440	0.049*
C8	0.41836 (17)	0.06983 (13)	0.35178 (14)	0.0464 (5)
H8	0.4168	0.0148	0.3768	0.056*
C9	0.3879 (2)	0.13137 (16)	0.41644 (16)	0.0563 (6)
H9A	0.3345	0.1088	0.4404	0.068*
H9B	0.3614	0.1811	0.3822	0.068*
C10	0.58938 (19)	0.10727 (17)	0.44576 (16)	0.0620 (7)
H10A	0.6426	0.1462	0.4431	0.074*
H10B	0.6239	0.0584	0.4771	0.074*
C11	0.52525 (15)	0.14001 (12)	0.27129 (13)	0.0396 (4)
C12	0.61175 (16)	0.10467 (13)	0.22990 (14)	0.0440 (5)
C13	0.68351 (17)	0.17114 (14)	0.22579 (15)	0.0483 (5)
C14	0.76778 (19)	0.17436 (18)	0.19293 (18)	0.0629 (7)
H14	0.7881	0.1289	0.1658	0.076*
C15	0.8227 (2)	0.2483 (2)	0.2014 (2)	0.0766 (8)
H15	0.8795	0.2514	0.1786	0.092*
C16	0.7955 (2)	0.3155 (2)	0.2419 (2)	0.0727 (8)
H16	0.8341	0.3631	0.2466	0.087*
C17	0.70888 (19)	0.31394 (16)	0.27714 (16)	0.0573 (6)
C18	0.65381 (17)	0.24013 (13)	0.26630 (14)	0.0458 (5)
C19	0.56458 (16)	0.22748 (13)	0.29537 (13)	0.0428 (4)
C20	0.53250 (19)	0.29075 (14)	0.33933 (15)	0.0534 (5)
H20	0.4753	0.2847	0.3612	0.064*
C21	0.5871 (2)	0.36550 (16)	0.35125 (17)	0.0656 (7)
H21	0.5644	0.4083	0.3808	0.079*
C22	0.6712 (2)	0.37727 (16)	0.32134 (18)	0.0690 (7)
H22	0.7044	0.4277	0.3301	0.083*
C31	0.35283 (16)	0.34577 (12)	0.11033 (15)	0.0415 (4)
H31	0.3258	0.3593	0.1588	0.050*
C32	0.36283 (15)	0.41397 (12)	0.04976 (15)	0.0413 (4)
C33	0.37847 (17)	0.49265 (13)	0.08745 (17)	0.0472 (5)
C34	0.38266 (18)	0.55894 (13)	0.0303 (2)	0.0552 (6)
C35	0.37141 (18)	0.54820 (15)	−0.0638 (2)	0.0604 (6)
H35	0.3748	0.5927	−0.1015	0.072*
C36	0.35523 (18)	0.47180 (16)	−0.10209 (17)	0.0592 (6)
H36	0.3468	0.4645	−0.1661	0.071*
C37	0.35122 (17)	0.40506 (14)	−0.04632 (15)	0.0496 (5)
H37	0.3406	0.3535	−0.0734	0.060*
C71	0.32874 (16)	−0.01146 (12)	0.20307 (15)	0.0429 (5)
C72	0.23750 (17)	−0.02650 (14)	0.12910 (16)	0.0478 (5)
C73	0.21611 (19)	−0.10360 (17)	0.08840 (18)	0.0594 (6)
C74	0.2840 (2)	−0.16626 (16)	0.1225 (2)	0.0692 (8)
H74	0.2687	−0.2180	0.0965	0.083*
C75	0.3744 (2)	−0.15297 (15)	0.1947 (2)	0.0652 (7)
H75	0.4206	−0.1958	0.2174	0.078*
C76	0.39782 (19)	−0.07630 (14)	0.23433 (17)	0.0514 (5)
H76	0.4605	−0.0679	0.2824	0.062*
N1	0.47866 (13)	0.15483 (10)	0.06896 (11)	0.0402 (4)
N2	0.52372 (14)	0.08807 (11)	0.35163 (12)	0.0465 (4)
O1	0.29640 (13)	0.23496 (9)	0.22163 (11)	0.0563 (4)
O2	0.62027 (13)	0.03332 (10)	0.21321 (12)	0.0564 (4)
S1	0.50629 (6)	0.15104 (5)	0.51224 (4)	0.0714 (2)
Cl1	0.40324 (7)	0.65580 (4)	0.07790 (7)	0.0925 (3)
Cl2	0.39619 (7)	0.50886 (4)	0.20618 (5)	0.0742 (2)
Cl3	0.14815 (5)	0.05119 (5)	0.08583 (4)	0.06758 (19)
Cl4	0.10393 (6)	−0.12156 (6)	−0.00563 (6)	0.0959 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0837 (17)	0.0490 (14)	0.0567 (13)	0.0021 (12)	0.0467 (13)	0.0001 (11)
C2	0.0610 (12)	0.0377 (11)	0.0381 (10)	−0.0020 (9)	0.0245 (9)	0.0068 (8)
C3	0.0423 (10)	0.0353 (10)	0.0344 (9)	0.0025 (8)	0.0137 (8)	0.0059 (8)
C4	0.0494 (11)	0.0343 (10)	0.0374 (9)	0.0048 (8)	0.0196 (8)	0.0061 (8)
C5	0.0461 (10)	0.0332 (10)	0.0357 (9)	0.0047 (8)	0.0206 (8)	0.0080 (8)
C6	0.0533 (11)	0.0345 (10)	0.0375 (10)	0.0000 (9)	0.0236 (8)	0.0034 (8)
C7	0.0495 (11)	0.0363 (11)	0.0432 (10)	0.0065 (9)	0.0255 (9)	0.0121 (8)
C8	0.0583 (12)	0.0453 (12)	0.0431 (11)	0.0087 (10)	0.0265 (9)	0.0156 (9)
C9	0.0683 (14)	0.0641 (15)	0.0459 (12)	0.0118 (12)	0.0313 (11)	0.0083 (11)
C10	0.0610 (14)	0.0774 (18)	0.0461 (12)	0.0138 (13)	0.0148 (11)	0.0228 (12)
C11	0.0482 (11)	0.0379 (11)	0.0382 (10)	0.0074 (9)	0.0214 (8)	0.0092 (8)
C12	0.0480 (11)	0.0435 (12)	0.0450 (11)	0.0100 (9)	0.0211 (9)	0.0103 (9)
C13	0.0475 (11)	0.0547 (14)	0.0446 (11)	0.0017 (10)	0.0174 (9)	0.0104 (10)
C14	0.0561 (14)	0.0755 (18)	0.0646 (15)	0.0006 (13)	0.0296 (12)	0.0099 (13)
C15	0.0562 (15)	0.098 (2)	0.0785 (19)	−0.0172 (16)	0.0261 (14)	0.0165 (17)
C16	0.0634 (16)	0.080 (2)	0.0665 (17)	−0.0250 (15)	0.0085 (13)	0.0184 (15)
C17	0.0619 (14)	0.0559 (15)	0.0437 (12)	−0.0120 (12)	0.0013 (10)	0.0098 (11)
C18	0.0522 (12)	0.0469 (12)	0.0339 (10)	−0.0031 (10)	0.0070 (8)	0.0089 (9)
C19	0.0538 (11)	0.0418 (11)	0.0307 (9)	0.0047 (9)	0.0102 (8)	0.0047 (8)
C20	0.0686 (14)	0.0511 (14)	0.0378 (11)	0.0050 (11)	0.0128 (10)	−0.0024 (9)
C21	0.0901 (19)	0.0516 (15)	0.0433 (13)	0.0025 (14)	0.0040 (12)	−0.0094 (11)
C22	0.0867 (19)	0.0518 (15)	0.0507 (14)	−0.0143 (14)	−0.0040 (13)	0.0002 (12)
C31	0.0463 (11)	0.0370 (10)	0.0442 (10)	0.0038 (9)	0.0183 (9)	0.0072 (8)
C32	0.0364 (10)	0.0361 (11)	0.0516 (11)	0.0050 (8)	0.0143 (8)	0.0130 (9)
C33	0.0468 (11)	0.0374 (11)	0.0657 (14)	0.0074 (9)	0.0296 (10)	0.0090 (10)
C34	0.0510 (12)	0.0341 (11)	0.0902 (18)	0.0091 (9)	0.0362 (12)	0.0152 (11)
C35	0.0541 (13)	0.0483 (14)	0.0783 (17)	0.0040 (11)	0.0201 (12)	0.0310 (13)
C36	0.0576 (14)	0.0638 (16)	0.0494 (13)	−0.0051 (12)	0.0070 (10)	0.0232 (11)
C37	0.0497 (12)	0.0445 (12)	0.0492 (12)	−0.0017 (10)	0.0076 (9)	0.0136 (10)
C71	0.0522 (11)	0.0390 (11)	0.0464 (11)	0.0013 (9)	0.0282 (9)	0.0126 (9)
C72	0.0518 (12)	0.0490 (13)	0.0521 (12)	0.0009 (10)	0.0301 (10)	0.0098 (10)
C73	0.0576 (14)	0.0672 (17)	0.0669 (15)	−0.0173 (12)	0.0389 (12)	−0.0098 (13)
C74	0.0791 (19)	0.0475 (15)	0.100 (2)	−0.0135 (13)	0.0561 (17)	−0.0087 (14)
C75	0.0797 (18)	0.0418 (13)	0.0900 (19)	0.0077 (12)	0.0496 (16)	0.0099 (13)
C76	0.0593 (13)	0.0427 (12)	0.0599 (13)	0.0061 (10)	0.0297 (11)	0.0118 (10)
N1	0.0538 (10)	0.0355 (9)	0.0393 (8)	0.0006 (7)	0.0263 (7)	0.0027 (7)
N2	0.0515 (10)	0.0518 (11)	0.0400 (9)	0.0112 (8)	0.0200 (8)	0.0179 (8)
O1	0.0765 (11)	0.0468 (9)	0.0629 (10)	0.0195 (8)	0.0467 (9)	0.0158 (7)
O2	0.0629 (10)	0.0446 (9)	0.0716 (11)	0.0134 (8)	0.0350 (8)	0.0075 (8)
S1	0.0871 (5)	0.0879 (5)	0.0392 (3)	0.0115 (4)	0.0196 (3)	0.0053 (3)
Cl1	0.1250 (7)	0.0333 (3)	0.1559 (8)	0.0032 (4)	0.0966 (6)	0.0036 (4)
Cl2	0.1147 (6)	0.0493 (4)	0.0793 (5)	0.0010 (3)	0.0602 (4)	−0.0074 (3)
Cl3	0.0641 (4)	0.0812 (5)	0.0562 (3)	0.0167 (3)	0.0171 (3)	0.0173 (3)
Cl4	0.0685 (4)	0.1288 (8)	0.0955 (6)	−0.0296 (5)	0.0332 (4)	−0.0408 (5)

Geometric parameters (Å, º)

C1—N1	1.459 (2)	C14—H14	0.9300
C1—H1A	0.9600	C15—C16	1.361 (4)
C1—H1B	0.9600	C15—H15	0.9300
C1—H1C	0.9600	C16—C17	1.421 (4)
C2—N1	1.457 (3)	C16—H16	0.9300
C2—C3	1.503 (3)	C17—C18	1.404 (3)
C2—H2A	0.9700	C17—C22	1.407 (4)
C2—H2B	0.9700	C18—C19	1.414 (3)
C3—C31	1.335 (3)	C19—C20	1.368 (3)
C3—C4	1.503 (2)	C20—C21	1.414 (4)
C4—O1	1.208 (2)	C20—H20	0.9300
C4—C5	1.539 (3)	C21—C22	1.354 (4)
C5—C6	1.533 (3)	C21—H21	0.9300
C5—C7	1.570 (2)	C22—H22	0.9300
C5—C11	1.595 (3)	C31—C32	1.470 (3)
C6—N1	1.452 (2)	C31—H31	0.9300
C6—H6A	0.9700	C32—C37	1.395 (3)
C6—H6B	0.9700	C32—C33	1.398 (3)
C7—C71	1.511 (3)	C33—C34	1.394 (3)
C7—C8	1.531 (3)	C33—Cl2	1.726 (2)
C7—H7	0.9800	C34—C35	1.370 (4)
C8—N2	1.451 (3)	C34—Cl1	1.728 (3)
C8—C9	1.537 (3)	C35—C36	1.367 (4)
C8—H8	0.9800	C35—H35	0.9300
C9—S1	1.804 (3)	C36—C37	1.386 (3)
C9—H9A	0.9700	C36—H36	0.9300
C9—H9B	0.9700	C37—H37	0.9300
C10—N2	1.437 (3)	C71—C72	1.391 (3)
C10—S1	1.855 (3)	C71—C76	1.395 (3)
C10—H10A	0.9700	C72—C73	1.394 (3)
C10—H10B	0.9700	C72—Cl3	1.734 (2)
C11—N2	1.473 (2)	C73—C74	1.365 (4)
C11—C19	1.535 (3)	C73—Cl4	1.733 (3)
C11—C12	1.588 (3)	C74—C75	1.366 (4)
C12—O2	1.211 (3)	C74—H74	0.9300
C12—C13	1.472 (3)	C75—C76	1.384 (4)
C13—C14	1.370 (3)	C75—H75	0.9300
C13—C18	1.399 (3)	C76—H76	0.9300
C14—C15	1.408 (4)
N1—C1—H1A	109.5	C16—C15—H15	118.9
N1—C1—H1B	109.5	C14—C15—H15	118.9
H1A—C1—H1B	109.5	C15—C16—C17	121.0 (3)
N1—C1—H1C	109.5	C15—C16—H16	119.5
H1A—C1—H1C	109.5	C17—C16—H16	119.5
H1B—C1—H1C	109.5	C18—C17—C22	115.9 (2)
N1—C2—C3	112.72 (15)	C18—C17—C16	116.0 (3)
N1—C2—H2A	109.0	C22—C17—C16	128.1 (3)
C3—C2—H2A	109.0	C13—C18—C17	122.5 (2)
N1—C2—H2B	109.0	C13—C18—C19	113.43 (19)
C3—C2—H2B	109.0	C17—C18—C19	124.1 (2)
H2A—C2—H2B	107.8	C20—C19—C18	117.4 (2)
C31—C3—C2	125.52 (17)	C20—C19—C11	133.3 (2)
C31—C3—C4	115.49 (17)	C18—C19—C11	109.31 (17)
C2—C3—C4	118.99 (16)	C19—C20—C21	119.3 (2)
O1—C4—C3	120.65 (17)	C19—C20—H20	120.3
O1—C4—C5	121.74 (16)	C21—C20—H20	120.3
C3—C4—C5	117.61 (15)	C22—C21—C20	122.6 (2)
C6—C5—C4	106.53 (15)	C22—C21—H21	118.7
C6—C5—C7	113.74 (16)	C20—C21—H21	118.7
C4—C5—C7	109.71 (15)	C21—C22—C17	120.6 (2)
C6—C5—C11	111.09 (15)	C21—C22—H22	119.7
C4—C5—C11	110.02 (16)	C17—C22—H22	119.7
C7—C5—C11	105.77 (14)	C3—C31—C32	129.57 (19)
N1—C6—C5	107.63 (16)	C3—C31—H31	115.2
N1—C6—H6A	110.2	C32—C31—H31	115.2
C5—C6—H6A	110.2	C37—C32—C33	117.51 (19)
N1—C6—H6B	110.2	C37—C32—C31	123.03 (19)
C5—C6—H6B	110.2	C33—C32—C31	119.35 (19)
H6A—C6—H6B	108.5	C34—C33—C32	120.5 (2)
C71—C7—C8	113.34 (16)	C34—C33—Cl2	118.97 (18)
C71—C7—C5	114.06 (15)	C32—C33—Cl2	120.51 (16)
C8—C7—C5	105.01 (16)	C35—C34—C33	120.6 (2)
C71—C7—H7	108.1	C35—C34—Cl1	119.29 (18)
C8—C7—H7	108.1	C33—C34—Cl1	120.1 (2)
C5—C7—H7	108.1	C36—C35—C34	119.7 (2)
N2—C8—C7	105.32 (15)	C36—C35—H35	120.2
N2—C8—C9	108.56 (19)	C34—C35—H35	120.2
C7—C8—C9	115.32 (18)	C35—C36—C37	120.5 (2)
N2—C8—H8	109.2	C35—C36—H36	119.7
C7—C8—H8	109.2	C37—C36—H36	119.7
C9—C8—H8	109.2	C36—C37—C32	121.1 (2)
C8—C9—S1	105.55 (16)	C36—C37—H37	119.4
C8—C9—H9A	110.6	C32—C37—H37	119.4
S1—C9—H9A	110.6	C72—C71—C76	117.4 (2)
C8—C9—H9B	110.6	C72—C71—C7	120.84 (19)
S1—C9—H9B	110.6	C76—C71—C7	121.8 (2)
H9A—C9—H9B	108.8	C71—C72—C73	121.1 (2)
N2—C10—S1	108.29 (16)	C71—C72—Cl3	120.10 (18)
N2—C10—H10A	110.0	C73—C72—Cl3	118.84 (19)
S1—C10—H10A	110.0	C74—C73—C72	120.0 (2)
N2—C10—H10B	110.0	C74—C73—Cl4	119.0 (2)
S1—C10—H10B	110.0	C72—C73—Cl4	121.0 (2)
H10A—C10—H10B	108.4	C73—C74—C75	120.0 (3)
N2—C11—C19	116.40 (16)	C73—C74—H74	120.0
N2—C11—C12	107.49 (15)	C75—C74—H74	120.0
C19—C11—C12	101.01 (16)	C74—C75—C76	120.6 (2)
N2—C11—C5	103.67 (15)	C74—C75—H75	119.7
C19—C11—C5	116.38 (15)	C76—C75—H75	119.7
C12—C11—C5	111.81 (16)	C75—C76—C71	120.9 (2)
O2—C12—C13	127.14 (19)	C75—C76—H76	119.6
O2—C12—C11	124.14 (18)	C71—C76—H76	119.6
C13—C12—C11	108.42 (18)	C6—N1—C2	110.74 (15)
C14—C13—C18	120.2 (2)	C6—N1—C1	112.68 (16)
C14—C13—C12	132.2 (2)	C2—N1—C1	110.85 (16)
C18—C13—C12	107.62 (18)	C10—N2—C8	110.36 (16)
C13—C14—C15	118.2 (3)	C10—N2—C11	120.12 (19)
C13—C14—H14	120.9	C8—N2—C11	112.51 (15)
C15—C14—H14	120.9	C9—S1—C10	92.41 (11)
C16—C15—C14	122.1 (3)
N1—C2—C3—C31	156.45 (19)	C12—C11—C19—C20	−174.7 (2)
N1—C2—C3—C4	−23.3 (3)	C5—C11—C19—C20	64.0 (3)
C31—C3—C4—O1	18.7 (3)	N2—C11—C19—C18	119.38 (18)
C2—C3—C4—O1	−161.5 (2)	C12—C11—C19—C18	3.37 (19)
C31—C3—C4—C5	−161.80 (18)	C5—C11—C19—C18	−117.89 (17)
C2—C3—C4—C5	18.0 (3)	C18—C19—C20—C21	1.7 (3)
O1—C4—C5—C6	142.8 (2)	C11—C19—C20—C21	179.7 (2)
C3—C4—C5—C6	−36.6 (2)	C19—C20—C21—C22	−0.5 (4)
O1—C4—C5—C7	19.3 (3)	C20—C21—C22—C17	−0.7 (4)
C3—C4—C5—C7	−160.15 (17)	C18—C17—C22—C21	0.4 (3)
O1—C4—C5—C11	−96.7 (2)	C16—C17—C22—C21	−179.8 (2)
C3—C4—C5—C11	83.9 (2)	C2—C3—C31—C32	0.7 (4)
C4—C5—C6—N1	63.73 (19)	C4—C3—C31—C32	−179.50 (19)
C7—C5—C6—N1	−175.29 (16)	C3—C31—C32—C37	32.4 (3)
C11—C5—C6—N1	−56.1 (2)	C3—C31—C32—C33	−151.6 (2)
C6—C5—C7—C71	12.5 (2)	C37—C32—C33—C34	−0.3 (3)
C4—C5—C7—C71	131.64 (18)	C31—C32—C33—C34	−176.58 (19)
C11—C5—C7—C71	−109.73 (18)	C37—C32—C33—Cl2	−178.69 (16)
C6—C5—C7—C8	137.12 (17)	C31—C32—C33—Cl2	5.1 (3)
C4—C5—C7—C8	−103.69 (18)	C32—C33—C34—C35	0.1 (3)
C11—C5—C7—C8	14.93 (19)	Cl2—C33—C34—C35	178.45 (18)
C71—C7—C8—N2	99.21 (19)	C32—C33—C34—Cl1	−179.40 (16)
C5—C7—C8—N2	−25.9 (2)	Cl2—C33—C34—Cl1	−1.0 (3)
C71—C7—C8—C9	−141.15 (19)	C33—C34—C35—C36	0.4 (4)
C5—C7—C8—C9	93.7 (2)	Cl1—C34—C35—C36	179.92 (18)
N2—C8—C9—S1	−35.39 (19)	C34—C35—C36—C37	−0.7 (4)
C7—C8—C9—S1	−153.24 (15)	C35—C36—C37—C32	0.4 (3)
C6—C5—C11—N2	−122.64 (16)	C33—C32—C37—C36	0.1 (3)
C4—C5—C11—N2	119.64 (16)	C31—C32—C37—C36	176.2 (2)
C7—C5—C11—N2	1.22 (19)	C8—C7—C71—C72	151.08 (18)
C6—C5—C11—C19	108.20 (18)	C5—C7—C71—C72	−88.8 (2)
C4—C5—C11—C19	−9.5 (2)	C8—C7—C71—C76	−28.6 (2)
C7—C5—C11—C19	−127.93 (16)	C5—C7—C71—C76	91.5 (2)
C6—C5—C11—C12	−7.1 (2)	C76—C71—C72—C73	0.3 (3)
C4—C5—C11—C12	−124.86 (16)	C7—C71—C72—C73	−179.33 (18)
C7—C5—C11—C12	116.72 (16)	C76—C71—C72—Cl3	−179.60 (15)
N2—C11—C12—O2	47.1 (3)	C7—C71—C72—Cl3	0.8 (2)
C19—C11—C12—O2	169.6 (2)	C71—C72—C73—C74	1.5 (3)
C5—C11—C12—O2	−66.0 (2)	Cl3—C72—C73—C74	−178.57 (18)
N2—C11—C12—C13	−126.97 (18)	C71—C72—C73—Cl4	−178.42 (15)
C19—C11—C12—C13	−4.5 (2)	Cl3—C72—C73—Cl4	1.5 (2)
C5—C11—C12—C13	119.88 (18)	C72—C73—C74—C75	−1.9 (4)
O2—C12—C13—C14	9.0 (4)	Cl4—C73—C74—C75	178.08 (19)
C11—C12—C13—C14	−177.1 (2)	C73—C74—C75—C76	0.4 (4)
O2—C12—C13—C18	−169.7 (2)	C74—C75—C76—C71	1.5 (3)
C11—C12—C13—C18	4.2 (2)	C72—C71—C76—C75	−1.8 (3)
C18—C13—C14—C15	0.1 (4)	C7—C71—C76—C75	177.82 (19)
C12—C13—C14—C15	−178.5 (2)	C5—C6—N1—C2	−74.49 (19)
C13—C14—C15—C16	0.9 (4)	C5—C6—N1—C1	160.69 (18)
C14—C15—C16—C17	−0.5 (4)	C3—C2—N1—C6	51.4 (2)
C15—C16—C17—C18	−0.8 (4)	C3—C2—N1—C1	177.21 (18)
C15—C16—C17—C22	179.4 (3)	S1—C10—N2—C8	−28.3 (2)
C14—C13—C18—C17	−1.5 (3)	S1—C10—N2—C11	105.10 (18)
C12—C13—C18—C17	177.43 (18)	C7—C8—N2—C10	166.02 (18)
C14—C13—C18—C19	179.1 (2)	C9—C8—N2—C10	42.0 (2)
C12—C13—C18—C19	−2.0 (2)	C7—C8—N2—C11	28.9 (2)
C22—C17—C18—C13	−178.4 (2)	C9—C8—N2—C11	−95.2 (2)
C16—C17—C18—C13	1.8 (3)	C19—C11—N2—C10	−22.0 (3)
C22—C17—C18—C19	1.0 (3)	C12—C11—N2—C10	90.3 (2)
C16—C17—C18—C19	−178.8 (2)	C5—C11—N2—C10	−151.19 (18)
C13—C18—C19—C20	177.38 (19)	C19—C11—N2—C8	110.5 (2)
C17—C18—C19—C20	−2.1 (3)	C12—C11—N2—C8	−137.21 (18)
C13—C18—C19—C11	−1.1 (2)	C5—C11—N2—C8	−18.7 (2)
C17—C18—C19—C11	179.47 (18)	C8—C9—S1—C10	16.34 (17)
N2—C11—C19—C20	−58.7 (3)	N2—C10—S1—C9	5.83 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C74—H74···Cl1^i	0.93	2.82	3.497 (3)	130
C2—H2B···Cl1^ii	0.97	2.86	3.784 (2)	159
C9—H9B···O1	0.97	2.44	3.251 (3)	141

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

(II) 5''-[(E)-4-fluorobenzylidene]-7'-(4-fluorophenyl)-1''-methyl- dispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''- piperidine]-2,4''-dione

Crystal data

C35H28F2N2O2S	F(000) = 1208
Mr = 578.65	Dx = 1.361 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2000 reflections
a = 14.8802 (5) Å	θ = 1.5–26°
b = 9.6789 (3) Å	µ = 0.16 mm^−1
c = 20.2209 (6) Å	T = 293 K
β = 104.155 (2)°	Block, colourless
V = 2823.87 (15) Å^3	0.21 × 0.14 × 0.11 mm
Z = 4

Data collection

Bruker Kappa APEXII area-detector diffractometer	5494 independent reflections
Radiation source: fine-focus sealed tube	3862 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 0 pixels mm^-1	θmax = 25.9°, θmin = 1.5°
ω and ϕ scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→11
Tmin = 0.973, Tmax = 0.982	l = −24→24
26085 measured reflections

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)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0681P)^2 + 0.8519P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
5494 reflections	Δρmax = 0.48 e Å^−3
381 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0062 (9)

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
C1	−0.15305 (18)	0.4448 (3)	0.28225 (12)	0.0628 (7)
H1A	−0.1707	0.5028	0.2427	0.094*
H1B	−0.1336	0.5014	0.3222	0.094*
H1C	−0.2050	0.3893	0.2861	0.094*
C2	−0.04196 (17)	0.2760 (3)	0.33779 (11)	0.0526 (6)
H2A	−0.0934	0.2289	0.3497	0.063*
H2B	−0.0154	0.3391	0.3747	0.063*
C3	0.03002 (15)	0.1710 (2)	0.33207 (10)	0.0440 (5)
C4	0.03833 (15)	0.1274 (2)	0.26293 (10)	0.0426 (5)
C5	−0.00577 (14)	0.2209 (2)	0.20305 (10)	0.0397 (5)
C6	−0.09805 (15)	0.2694 (2)	0.21522 (10)	0.0460 (5)
H6A	−0.1324	0.3218	0.1763	0.055*
H6B	−0.1352	0.1907	0.2218	0.055*
C7	−0.01536 (15)	0.1480 (2)	0.13307 (10)	0.0425 (5)
H7	0.0380	0.0861	0.1383	0.051*
C8	0.00041 (15)	0.2671 (2)	0.08807 (10)	0.0434 (5)
H8	−0.0529	0.3299	0.0784	0.052*
C9	0.03157 (17)	0.2363 (3)	0.02334 (11)	0.0538 (6)
H9A	−0.0212	0.2323	−0.0158	0.065*
H9B	0.0643	0.1489	0.0273	0.065*
C10	0.11424 (17)	0.4438 (2)	0.10004 (11)	0.0511 (6)
H10A	0.1776	0.4664	0.1233	0.061*
H10B	0.0760	0.5255	0.0983	0.061*
C11	0.06113 (14)	0.3493 (2)	0.20044 (10)	0.0395 (5)
C12	0.01502 (16)	0.4921 (2)	0.20905 (11)	0.0451 (5)
C13	0.07251 (16)	0.5604 (2)	0.27009 (11)	0.0448 (5)
C14	0.06570 (19)	0.6845 (2)	0.30091 (13)	0.0584 (6)
H14	0.0162	0.7439	0.2842	0.070*
C15	0.1360 (2)	0.7188 (3)	0.35860 (14)	0.0653 (7)
H15	0.1316	0.8023	0.3804	0.078*
C16	0.21030 (19)	0.6362 (3)	0.38422 (13)	0.0590 (6)
H16	0.2546	0.6636	0.4229	0.071*
C17	0.22073 (16)	0.5089 (2)	0.35240 (11)	0.0475 (5)
C18	0.14907 (15)	0.4749 (2)	0.29564 (10)	0.0408 (5)
C19	0.14965 (14)	0.3552 (2)	0.25671 (10)	0.0391 (5)
C20	0.22503 (15)	0.2704 (2)	0.27270 (11)	0.0469 (5)
H20	0.2286	0.1926	0.2464	0.056*
C21	0.29749 (16)	0.3028 (3)	0.32984 (12)	0.0553 (6)
H21	0.3487	0.2446	0.3410	0.066*
C22	0.29525 (17)	0.4159 (3)	0.36932 (12)	0.0547 (6)
H22	0.3433	0.4317	0.4077	0.066*
C31	0.08855 (15)	0.1105 (2)	0.38478 (11)	0.0473 (5)
H31	0.1300	0.0503	0.3721	0.057*
C32	0.10033 (15)	0.1204 (2)	0.45840 (11)	0.0481 (5)
C33	0.17584 (18)	0.0539 (3)	0.49983 (13)	0.0620 (7)
H33	0.2170	0.0075	0.4796	0.074*
C34	0.1922 (2)	0.0538 (3)	0.56959 (14)	0.0740 (8)
H34	0.2434	0.0084	0.5964	0.089*
C35	0.1319 (2)	0.1217 (3)	0.59849 (13)	0.0746 (8)
C36	0.0567 (2)	0.1887 (4)	0.56072 (13)	0.0825 (9)
H36	0.0167	0.2355	0.5819	0.099*
C37	0.04015 (17)	0.1868 (3)	0.49091 (12)	0.0675 (7)
H37	−0.0122	0.2307	0.4649	0.081*
C71	−0.10051 (15)	0.0609 (2)	0.10814 (11)	0.0462 (5)
C72	−0.09766 (18)	−0.0775 (3)	0.12764 (12)	0.0564 (6)
H72	−0.0434	−0.1129	0.1556	0.068*
C73	−0.1730 (2)	−0.1630 (3)	0.10651 (14)	0.0682 (7)
H73	−0.1705	−0.2552	0.1198	0.082*
C74	−0.2504 (2)	−0.1093 (3)	0.06597 (14)	0.0680 (8)
C75	−0.25793 (19)	0.0247 (3)	0.04460 (14)	0.0726 (8)
H75	−0.3127	0.0579	0.0164	0.087*
C76	−0.18107 (17)	0.1106 (3)	0.06630 (13)	0.0593 (6)
H76	−0.1844	0.2024	0.0523	0.071*
N1	−0.07726 (12)	0.35567 (18)	0.27589 (9)	0.0449 (4)
N2	0.07968 (12)	0.33167 (18)	0.13352 (8)	0.0420 (4)
O1	0.07782 (13)	0.02157 (16)	0.25485 (8)	0.0607 (5)
O2	−0.04921 (12)	0.54203 (17)	0.16689 (8)	0.0586 (4)
F1	0.14657 (15)	0.1233 (3)	0.66720 (8)	0.1217 (8)
F2	−0.32629 (13)	−0.1920 (2)	0.04365 (10)	0.1034 (7)
S1	0.10793 (4)	0.37798 (7)	0.01481 (3)	0.0552 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0607 (15)	0.0769 (18)	0.0505 (14)	0.0242 (13)	0.0131 (12)	−0.0035 (12)
C2	0.0560 (13)	0.0648 (15)	0.0383 (11)	0.0108 (12)	0.0136 (10)	0.0034 (10)
C3	0.0480 (12)	0.0453 (12)	0.0404 (11)	0.0011 (10)	0.0138 (9)	0.0038 (9)
C4	0.0470 (12)	0.0398 (12)	0.0417 (11)	−0.0001 (10)	0.0126 (9)	0.0022 (9)
C5	0.0454 (11)	0.0393 (11)	0.0348 (10)	0.0023 (9)	0.0104 (8)	−0.0021 (9)
C6	0.0454 (12)	0.0537 (13)	0.0381 (11)	0.0031 (10)	0.0089 (9)	−0.0017 (9)
C7	0.0466 (12)	0.0436 (12)	0.0374 (11)	0.0009 (9)	0.0106 (9)	−0.0036 (9)
C8	0.0453 (11)	0.0482 (12)	0.0349 (10)	0.0007 (10)	0.0063 (9)	−0.0025 (9)
C9	0.0581 (14)	0.0673 (15)	0.0351 (11)	−0.0061 (12)	0.0096 (10)	−0.0057 (10)
C10	0.0577 (14)	0.0544 (14)	0.0416 (12)	−0.0057 (11)	0.0131 (10)	0.0016 (10)
C11	0.0464 (12)	0.0401 (11)	0.0318 (10)	0.0051 (9)	0.0091 (9)	0.0003 (8)
C12	0.0549 (13)	0.0422 (12)	0.0398 (11)	0.0069 (10)	0.0146 (10)	0.0051 (9)
C13	0.0582 (13)	0.0355 (11)	0.0435 (11)	0.0006 (10)	0.0181 (10)	0.0006 (9)
C14	0.0753 (17)	0.0395 (13)	0.0657 (16)	0.0041 (12)	0.0274 (13)	−0.0011 (11)
C15	0.091 (2)	0.0437 (14)	0.0672 (16)	−0.0131 (14)	0.0306 (15)	−0.0191 (12)
C16	0.0729 (17)	0.0557 (15)	0.0497 (13)	−0.0208 (13)	0.0177 (12)	−0.0134 (11)
C17	0.0584 (14)	0.0470 (12)	0.0385 (11)	−0.0151 (11)	0.0147 (10)	−0.0033 (9)
C18	0.0517 (12)	0.0377 (11)	0.0355 (10)	−0.0048 (9)	0.0152 (9)	0.0012 (8)
C19	0.0459 (11)	0.0379 (11)	0.0339 (10)	−0.0006 (9)	0.0104 (9)	0.0002 (8)
C20	0.0496 (12)	0.0464 (12)	0.0451 (12)	0.0052 (10)	0.0122 (10)	−0.0006 (10)
C21	0.0469 (13)	0.0612 (15)	0.0548 (14)	0.0025 (11)	0.0066 (11)	0.0067 (12)
C22	0.0515 (13)	0.0643 (15)	0.0437 (12)	−0.0099 (12)	0.0032 (10)	0.0031 (11)
C31	0.0483 (12)	0.0472 (12)	0.0468 (12)	0.0042 (10)	0.0124 (10)	0.0026 (10)
C32	0.0469 (12)	0.0524 (13)	0.0424 (12)	0.0000 (10)	0.0059 (10)	0.0032 (10)
C33	0.0619 (15)	0.0652 (16)	0.0517 (14)	0.0139 (13)	−0.0001 (12)	−0.0007 (12)
C34	0.0729 (18)	0.0817 (19)	0.0524 (15)	0.0126 (15)	−0.0137 (13)	0.0029 (14)
C35	0.0754 (18)	0.102 (2)	0.0390 (13)	0.0051 (17)	0.0005 (13)	0.0028 (14)
C36	0.0679 (18)	0.136 (3)	0.0450 (14)	0.0186 (19)	0.0168 (13)	0.0017 (16)
C37	0.0514 (14)	0.104 (2)	0.0466 (13)	0.0177 (14)	0.0109 (11)	0.0116 (14)
C71	0.0516 (13)	0.0489 (13)	0.0403 (11)	−0.0025 (10)	0.0152 (10)	−0.0103 (10)
C72	0.0661 (15)	0.0523 (14)	0.0533 (14)	−0.0057 (12)	0.0194 (12)	−0.0063 (11)
C73	0.085 (2)	0.0594 (16)	0.0663 (17)	−0.0181 (15)	0.0298 (15)	−0.0076 (13)
C74	0.0701 (18)	0.078 (2)	0.0645 (17)	−0.0332 (15)	0.0325 (15)	−0.0230 (15)
C75	0.0543 (15)	0.096 (2)	0.0642 (17)	−0.0046 (15)	0.0075 (13)	−0.0156 (16)
C76	0.0605 (15)	0.0585 (15)	0.0560 (14)	−0.0065 (12)	0.0087 (12)	−0.0085 (12)
N1	0.0460 (10)	0.0516 (11)	0.0368 (9)	0.0109 (8)	0.0095 (8)	−0.0017 (8)
N2	0.0495 (10)	0.0443 (10)	0.0325 (9)	−0.0027 (8)	0.0107 (7)	−0.0012 (7)
O1	0.0867 (13)	0.0467 (9)	0.0500 (9)	0.0194 (9)	0.0194 (9)	0.0030 (7)
O2	0.0676 (11)	0.0590 (10)	0.0465 (9)	0.0227 (8)	0.0085 (8)	0.0110 (8)
F1	0.1215 (16)	0.193 (2)	0.0394 (9)	0.0317 (16)	−0.0007 (9)	0.0023 (11)
F2	0.0879 (12)	0.1247 (16)	0.1008 (14)	−0.0592 (12)	0.0295 (10)	−0.0228 (12)
S1	0.0614 (4)	0.0676 (4)	0.0389 (3)	−0.0014 (3)	0.0164 (3)	0.0049 (3)

Geometric parameters (Å, º)

C1—N1	1.451 (3)	C14—H14	0.9300
C1—H1A	0.9600	C15—C16	1.360 (4)
C1—H1B	0.9600	C15—H15	0.9300
C1—H1C	0.9600	C16—C17	1.416 (3)
C2—N1	1.455 (3)	C16—H16	0.9300
C2—C3	1.502 (3)	C17—C18	1.402 (3)
C2—H2A	0.9700	C17—C22	1.404 (3)
C2—H2B	0.9700	C18—C19	1.402 (3)
C3—C31	1.335 (3)	C19—C20	1.364 (3)
C3—C4	1.494 (3)	C20—C21	1.409 (3)
C4—O1	1.211 (2)	C20—H20	0.9300
C4—C5	1.525 (3)	C21—C22	1.360 (3)
C5—C6	1.527 (3)	C21—H21	0.9300
C5—C7	1.556 (3)	C22—H22	0.9300
C5—C11	1.602 (3)	C31—C32	1.459 (3)
C6—N1	1.453 (3)	C31—H31	0.9300
C6—H6A	0.9700	C32—C33	1.385 (3)
C6—H6B	0.9700	C32—C37	1.391 (3)
C7—C71	1.503 (3)	C33—C34	1.371 (4)
C7—C8	1.522 (3)	C33—H33	0.9300
C7—H7	0.9800	C34—C35	1.354 (4)
C8—N2	1.448 (3)	C34—H34	0.9300
C8—C9	1.521 (3)	C35—F1	1.353 (3)
C8—H8	0.9800	C35—C36	1.356 (4)
C9—S1	1.816 (2)	C36—C37	1.372 (3)
C9—H9A	0.9700	C36—H36	0.9300
C9—H9B	0.9700	C37—H37	0.9300
C10—N2	1.439 (3)	C71—C76	1.374 (3)
C10—S1	1.818 (2)	C71—C72	1.394 (3)
C10—H10A	0.9700	C72—C73	1.375 (4)
C10—H10B	0.9700	C72—H72	0.9300
C11—N2	1.456 (2)	C73—C74	1.345 (4)
C11—C19	1.517 (3)	C73—H73	0.9300
C11—C12	1.571 (3)	C74—C75	1.363 (4)
C12—O2	1.215 (3)	C74—F2	1.368 (3)
C12—C13	1.475 (3)	C75—C76	1.395 (4)
C13—C14	1.368 (3)	C75—H75	0.9300
C13—C18	1.401 (3)	C76—H76	0.9300
C14—C15	1.403 (4)
N1—C1—H1A	109.5	C16—C15—H15	118.3
N1—C1—H1B	109.5	C14—C15—H15	118.3
H1A—C1—H1B	109.5	C15—C16—C17	120.5 (2)
N1—C1—H1C	109.5	C15—C16—H16	119.7
H1A—C1—H1C	109.5	C17—C16—H16	119.7
H1B—C1—H1C	109.5	C18—C17—C22	116.5 (2)
N1—C2—C3	114.02 (17)	C18—C17—C16	115.5 (2)
N1—C2—H2A	108.7	C22—C17—C16	128.0 (2)
C3—C2—H2A	108.7	C13—C18—C17	123.4 (2)
N1—C2—H2B	108.7	C13—C18—C19	113.43 (19)
C3—C2—H2B	108.7	C17—C18—C19	123.1 (2)
H2A—C2—H2B	107.6	C20—C19—C18	118.83 (19)
C31—C3—C4	115.86 (19)	C20—C19—C11	131.96 (18)
C31—C3—C2	124.99 (19)	C18—C19—C11	109.18 (17)
C4—C3—C2	119.14 (18)	C19—C20—C21	118.7 (2)
O1—C4—C3	121.25 (19)	C19—C20—H20	120.6
O1—C4—C5	121.54 (19)	C21—C20—H20	120.6
C3—C4—C5	117.21 (18)	C22—C21—C20	122.5 (2)
C4—C5—C6	106.49 (17)	C22—C21—H21	118.8
C4—C5—C7	112.26 (16)	C20—C21—H21	118.8
C6—C5—C7	113.58 (17)	C21—C22—C17	120.3 (2)
C4—C5—C11	109.66 (16)	C21—C22—H22	119.9
C6—C5—C11	110.91 (17)	C17—C22—H22	119.9
C7—C5—C11	103.97 (15)	C3—C31—C32	132.7 (2)
N1—C6—C5	107.38 (17)	C3—C31—H31	113.7
N1—C6—H6A	110.2	C32—C31—H31	113.7
C5—C6—H6A	110.2	C33—C32—C37	116.7 (2)
N1—C6—H6B	110.2	C33—C32—C31	117.7 (2)
C5—C6—H6B	110.2	C37—C32—C31	125.6 (2)
H6A—C6—H6B	108.5	C34—C33—C32	122.4 (3)
C71—C7—C8	117.72 (18)	C34—C33—H33	118.8
C71—C7—C5	116.22 (17)	C32—C33—H33	118.8
C8—C7—C5	101.95 (16)	C35—C34—C33	118.3 (2)
C71—C7—H7	106.7	C35—C34—H34	120.9
C8—C7—H7	106.7	C33—C34—H34	120.9
C5—C7—H7	106.7	F1—C35—C34	119.4 (3)
N2—C8—C9	104.97 (17)	F1—C35—C36	118.4 (3)
N2—C8—C7	99.68 (16)	C34—C35—C36	122.1 (2)
C9—C8—C7	119.33 (19)	C35—C36—C37	119.2 (3)
N2—C8—H8	110.7	C35—C36—H36	120.4
C9—C8—H8	110.7	C37—C36—H36	120.4
C7—C8—H8	110.7	C36—C37—C32	121.2 (2)
C8—C9—S1	105.25 (15)	C36—C37—H37	119.4
C8—C9—H9A	110.7	C32—C37—H37	119.4
S1—C9—H9A	110.7	C76—C71—C72	118.2 (2)
C8—C9—H9B	110.7	C76—C71—C7	123.2 (2)
S1—C9—H9B	110.7	C72—C71—C7	118.7 (2)
H9A—C9—H9B	108.8	C73—C72—C71	121.6 (3)
N2—C10—S1	103.89 (15)	C73—C72—H72	119.2
N2—C10—H10A	111.0	C71—C72—H72	119.2
S1—C10—H10A	111.0	C74—C73—C72	117.9 (3)
N2—C10—H10B	111.0	C74—C73—H73	121.0
S1—C10—H10B	111.0	C72—C73—H73	121.0
H10A—C10—H10B	109.0	C73—C74—C75	123.6 (3)
N2—C11—C19	112.00 (16)	C73—C74—F2	119.3 (3)
N2—C11—C12	113.18 (16)	C75—C74—F2	117.1 (3)
C19—C11—C12	101.93 (16)	C74—C75—C76	118.0 (3)
N2—C11—C5	101.54 (15)	C74—C75—H75	121.0
C19—C11—C5	115.91 (16)	C76—C75—H75	121.0
C12—C11—C5	112.78 (16)	C71—C76—C75	120.6 (3)
O2—C12—C13	127.2 (2)	C71—C76—H76	119.7
O2—C12—C11	124.19 (19)	C75—C76—H76	119.7
C13—C12—C11	107.90 (17)	C1—N1—C6	114.01 (17)
C14—C13—C18	119.7 (2)	C1—N1—C2	111.35 (17)
C14—C13—C12	133.0 (2)	C6—N1—C2	112.30 (17)
C18—C13—C12	107.25 (18)	C10—N2—C8	110.87 (16)
C13—C14—C15	117.6 (2)	C10—N2—C11	121.29 (17)
C13—C14—H14	121.2	C8—N2—C11	109.30 (16)
C15—C14—H14	121.2	C9—S1—C10	93.62 (10)
C16—C15—C14	123.3 (2)
N1—C2—C3—C31	162.5 (2)	C17—C18—C19—C20	−2.9 (3)
N1—C2—C3—C4	−18.0 (3)	C13—C18—C19—C11	−4.4 (2)
C31—C3—C4—O1	17.9 (3)	C17—C18—C19—C11	178.84 (18)
C2—C3—C4—O1	−161.6 (2)	N2—C11—C19—C20	−51.1 (3)
C31—C3—C4—C5	−162.70 (19)	C12—C11—C19—C20	−172.4 (2)
C2—C3—C4—C5	17.8 (3)	C5—C11—C19—C20	64.7 (3)
O1—C4—C5—C6	139.2 (2)	N2—C11—C19—C18	126.79 (18)
C3—C4—C5—C6	−40.2 (2)	C12—C11—C19—C18	5.5 (2)
O1—C4—C5—C7	14.3 (3)	C5—C11—C19—C18	−117.35 (18)
C3—C4—C5—C7	−165.13 (18)	C18—C19—C20—C21	3.1 (3)
O1—C4—C5—C11	−100.8 (2)	C11—C19—C20—C21	−179.2 (2)
C3—C4—C5—C11	79.8 (2)	C19—C20—C21—C22	−0.4 (3)
C4—C5—C6—N1	65.8 (2)	C20—C21—C22—C17	−2.6 (4)
C7—C5—C6—N1	−170.16 (17)	C18—C17—C22—C21	2.8 (3)
C11—C5—C6—N1	−53.5 (2)	C16—C17—C22—C21	−174.8 (2)
C4—C5—C7—C71	85.1 (2)	C4—C3—C31—C32	−177.4 (2)
C6—C5—C7—C71	−35.7 (3)	C2—C3—C31—C32	2.1 (4)
C11—C5—C7—C71	−156.39 (18)	C3—C31—C32—C33	−172.9 (3)
C4—C5—C7—C8	−145.50 (17)	C3—C31—C32—C37	9.6 (4)
C6—C5—C7—C8	93.6 (2)	C37—C32—C33—C34	−0.8 (4)
C11—C5—C7—C8	−27.04 (19)	C31—C32—C33—C34	−178.4 (3)
C71—C7—C8—N2	172.99 (17)	C32—C33—C34—C35	−0.1 (5)
C5—C7—C8—N2	44.58 (19)	C33—C34—C35—F1	−179.9 (3)
C71—C7—C8—C9	−73.7 (3)	C33—C34—C35—C36	0.1 (5)
C5—C7—C8—C9	157.93 (18)	F1—C35—C36—C37	−179.2 (3)
N2—C8—C9—S1	−34.8 (2)	C34—C35—C36—C37	0.7 (5)
C7—C8—C9—S1	−145.30 (17)	C35—C36—C37—C32	−1.6 (5)
C4—C5—C11—N2	119.78 (17)	C33—C32—C37—C36	1.6 (4)
C6—C5—C11—N2	−122.89 (17)	C31—C32—C37—C36	179.1 (3)
C7—C5—C11—N2	−0.45 (19)	C8—C7—C71—C76	−28.9 (3)
C4—C5—C11—C19	−1.8 (2)	C5—C7—C71—C76	92.4 (3)
C6—C5—C11—C19	115.50 (18)	C8—C7—C71—C72	150.4 (2)
C7—C5—C11—C19	−122.06 (18)	C5—C7—C71—C72	−88.3 (2)
C4—C5—C11—C12	−118.79 (18)	C76—C71—C72—C73	−0.5 (4)
C6—C5—C11—C12	−1.5 (2)	C7—C71—C72—C73	−179.8 (2)
C7—C5—C11—C12	120.98 (17)	C71—C72—C73—C74	0.1 (4)
N2—C11—C12—O2	45.7 (3)	C72—C73—C74—C75	0.3 (4)
C19—C11—C12—O2	166.1 (2)	C72—C73—C74—F2	179.5 (2)
C5—C11—C12—O2	−68.9 (3)	C73—C74—C75—C76	−0.3 (4)
N2—C11—C12—C13	−125.37 (18)	F2—C74—C75—C76	−179.4 (2)
C19—C11—C12—C13	−4.9 (2)	C72—C71—C76—C75	0.6 (4)
C5—C11—C12—C13	120.06 (18)	C7—C71—C76—C75	179.8 (2)
O2—C12—C13—C14	8.9 (4)	C74—C75—C76—C71	−0.2 (4)
C11—C12—C13—C14	179.6 (2)	C5—C6—N1—C1	161.16 (19)
O2—C12—C13—C18	−168.0 (2)	C5—C6—N1—C2	−71.0 (2)
C11—C12—C13—C18	2.7 (2)	C3—C2—N1—C1	174.0 (2)
C18—C13—C14—C15	−1.5 (3)	C3—C2—N1—C6	44.8 (3)
C12—C13—C14—C15	−178.1 (2)	S1—C10—N2—C8	−41.1 (2)
C13—C14—C15—C16	1.0 (4)	S1—C10—N2—C11	−171.31 (15)
C14—C15—C16—C17	0.8 (4)	C9—C8—N2—C10	51.0 (2)
C15—C16—C17—C18	−1.8 (3)	C7—C8—N2—C10	175.06 (17)
C15—C16—C17—C22	175.7 (2)	C9—C8—N2—C11	−172.74 (17)
C14—C13—C18—C17	0.3 (3)	C7—C8—N2—C11	−48.7 (2)
C12—C13—C18—C17	177.75 (19)	C19—C11—N2—C10	−74.3 (2)
C14—C13—C18—C19	−176.45 (19)	C12—C11—N2—C10	40.2 (3)
C12—C13—C18—C19	1.0 (2)	C5—C11—N2—C10	161.40 (18)
C22—C17—C18—C13	−176.5 (2)	C19—C11—N2—C8	154.81 (17)
C16—C17—C18—C13	1.3 (3)	C12—C11—N2—C8	−90.6 (2)
C22—C17—C18—C19	0.0 (3)	C5—C11—N2—C8	30.5 (2)
C16—C17—C18—C19	177.8 (2)	C8—C9—S1—C10	11.06 (17)
C13—C18—C19—C20	173.85 (19)	N2—C10—S1—C9	15.56 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C33—H33···S1^i	0.93	2.87	3.716 (3)	152
C37—H37···F2^ii	0.93	2.48	3.302 (3)	147
C73—H73···O2^iii	0.93	2.68	3.454 (4)	141
C10—H10B···O2	0.97	2.59	3.202 (3)	122

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

(III) 5''-[(E)-4-bromobenzylidene]-7'-(4-bromophenyl)-1''-methyl- dispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''- piperidine]-2,4''-dione

Crystal data

C35H28Br2N2O2S	F(000) = 1416
Mr = 700.47	Dx = 1.519 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 14.2275 (7) Å	θ = 1.6–26.3°
b = 15.6753 (8) Å	µ = 2.75 mm^−1
c = 15.3780 (7) Å	T = 293 K
β = 116.761 (2)°	Block, colourless
V = 3062.3 (3) Å^3	0.19 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker Kappa APEXII area-detector diffractometer	6169 independent reflections
Radiation source: fine-focus sealed tube	3897 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 0 pixels mm^-1	θmax = 26.3°, θmin = 1.6°
ω and ϕ scans	h = −15→17
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −19→19
Tmin = 0.599, Tmax = 0.739	l = −19→14
30894 measured reflections

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.0782P)^2 + 0.813P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
6169 reflections	Δρmax = 0.78 e Å^−3
382 parameters	Δρmin = −0.98 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0009 (3)

Special details

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

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
C1	0.0522 (3)	0.7463 (2)	0.3566 (2)	0.0519 (9)
H1A	0.0641	0.7343	0.3012	0.078*
H1B	0.0373	0.8059	0.3576	0.078*
H1C	−0.0064	0.7133	0.3527	0.078*
C2	0.2342 (2)	0.7785 (2)	0.4580 (2)	0.0407 (8)
H2A	0.2172	0.8372	0.4652	0.049*
H2B	0.2447	0.7752	0.4000	0.049*
C3	0.3348 (2)	0.7545 (2)	0.5448 (2)	0.0354 (7)
C4	0.3478 (2)	0.6663 (2)	0.5823 (2)	0.0342 (7)
C5	0.2472 (2)	0.61677 (18)	0.5600 (2)	0.0313 (7)
C6	0.1717 (2)	0.63488 (19)	0.4531 (2)	0.0346 (7)
H6A	0.2051	0.6211	0.4120	0.041*
H6B	0.1086	0.6005	0.4326	0.041*
C7	0.2676 (2)	0.52039 (18)	0.5842 (2)	0.0336 (7)
H7	0.3365	0.5152	0.6412	0.040*
C8	0.1849 (2)	0.49928 (18)	0.6169 (2)	0.0354 (7)
H8	0.1147	0.4994	0.5613	0.042*
C9	0.1985 (3)	0.4224 (2)	0.6800 (2)	0.0468 (8)
H9A	0.2721	0.4134	0.7248	0.056*
H9B	0.1711	0.3715	0.6408	0.056*
C10	0.1294 (3)	0.5631 (2)	0.7277 (2)	0.0463 (8)
H10A	0.0599	0.5860	0.6869	0.056*
H10B	0.1590	0.5929	0.7896	0.056*
C11	0.1964 (2)	0.64933 (19)	0.6283 (2)	0.0335 (7)
C12	0.0836 (3)	0.6875 (2)	0.5678 (2)	0.0404 (8)
C13	0.0850 (3)	0.7771 (2)	0.5966 (3)	0.0498 (9)
C17	0.2135 (4)	0.8732 (2)	0.7188 (3)	0.0637 (11)
C18	0.1846 (3)	0.7935 (2)	0.6715 (3)	0.0464 (9)
C19	0.2516 (3)	0.7227 (2)	0.6968 (2)	0.0382 (7)
C20	0.3488 (3)	0.7292 (2)	0.7742 (2)	0.0499 (9)
H20	0.3942	0.6827	0.7947	0.060*
C21	0.3789 (4)	0.8089 (3)	0.8225 (3)	0.0656 (12)
H21	0.4457	0.8139	0.8746	0.079*
C22	0.3155 (4)	0.8777 (3)	0.7968 (3)	0.0746 (13)
H22	0.3393	0.9286	0.8308	0.090*
C31	0.4114 (3)	0.8104 (2)	0.5942 (2)	0.0451 (8)
H31	0.4722	0.7884	0.6446	0.054*
C32	0.4099 (3)	0.9021 (2)	0.5777 (2)	0.0473 (8)
C33	0.4422 (3)	0.9576 (2)	0.6551 (3)	0.0574 (10)
H33	0.4732	0.9354	0.7180	0.069*
C34	0.4304 (4)	1.0443 (3)	0.6433 (3)	0.0707 (12)
H34	0.4505	1.0804	0.6967	0.085*
C35	0.3880 (3)	1.0763 (3)	0.5503 (3)	0.0741 (13)
C36	0.3618 (3)	1.0239 (3)	0.4717 (3)	0.0770 (14)
H36	0.3367	1.0470	0.4096	0.092*
C37	0.3726 (3)	0.9374 (3)	0.4846 (3)	0.0631 (11)
H37	0.3549	0.9019	0.4310	0.076*
C71	0.2699 (2)	0.46532 (18)	0.5044 (2)	0.0354 (7)
C72	0.3626 (2)	0.4520 (2)	0.4980 (2)	0.0412 (7)
H72	0.4244	0.4766	0.5444	0.049*
C73	0.3661 (3)	0.4031 (2)	0.4246 (3)	0.0467 (8)
H73	0.4291	0.3952	0.4211	0.056*
C74	0.2754 (3)	0.36683 (19)	0.3575 (2)	0.0448 (8)
C75	0.1838 (3)	0.3760 (2)	0.3631 (3)	0.0553 (10)
H75	0.1231	0.3492	0.3178	0.066*
C76	0.1805 (3)	0.4249 (2)	0.4360 (3)	0.0533 (9)
H76	0.1172	0.4310	0.4395	0.064*
N1	0.14538 (19)	0.72429 (16)	0.44495 (17)	0.0358 (6)
N2	0.19680 (19)	0.57135 (15)	0.68065 (17)	0.0365 (6)
O1	0.43404 (17)	0.63497 (14)	0.63004 (16)	0.0464 (6)
O2	0.00690 (17)	0.64512 (15)	0.51719 (16)	0.0505 (6)
S1	0.12300 (8)	0.44882 (6)	0.74531 (7)	0.0602 (3)
Br1	0.27782 (4)	0.30269 (3)	0.25388 (3)	0.0809 (2)
C14	0.0098 (4)	0.8396 (3)	0.5662 (3)	0.0730 (12)
H14	−0.0576	0.8292	0.5170	0.088*
C15	0.0372 (5)	0.9195 (3)	0.6112 (4)	0.0981 (17)
H15	−0.0130	0.9627	0.5907	0.118*
C16	0.1351 (6)	0.9362 (3)	0.6841 (4)	0.0937 (16)
H16	0.1502	0.9905	0.7114	0.112*
Br2	0.36431 (6)	1.19455 (3)	0.53017 (6)	0.1403 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.043 (2)	0.053 (2)	0.049 (2)	−0.0026 (17)	0.0116 (17)	0.0062 (17)
C2	0.0440 (19)	0.0400 (18)	0.0398 (18)	−0.0088 (14)	0.0205 (16)	0.0012 (14)
C3	0.0343 (17)	0.0421 (18)	0.0342 (16)	−0.0084 (14)	0.0195 (15)	−0.0024 (14)
C4	0.0352 (18)	0.0393 (17)	0.0320 (16)	−0.0067 (14)	0.0185 (15)	−0.0071 (13)
C5	0.0290 (16)	0.0350 (16)	0.0303 (15)	−0.0043 (12)	0.0138 (13)	−0.0037 (12)
C6	0.0359 (17)	0.0377 (17)	0.0312 (16)	−0.0058 (13)	0.0161 (14)	−0.0035 (13)
C7	0.0346 (17)	0.0317 (16)	0.0335 (16)	−0.0036 (13)	0.0146 (14)	−0.0022 (12)
C8	0.0373 (17)	0.0340 (17)	0.0330 (16)	−0.0044 (13)	0.0142 (14)	−0.0012 (13)
C9	0.056 (2)	0.0407 (19)	0.0434 (19)	−0.0095 (16)	0.0226 (17)	0.0021 (15)
C10	0.053 (2)	0.050 (2)	0.0432 (18)	−0.0112 (16)	0.0290 (17)	−0.0028 (15)
C11	0.0359 (17)	0.0354 (17)	0.0338 (16)	−0.0040 (13)	0.0197 (14)	−0.0024 (13)
C12	0.0402 (19)	0.046 (2)	0.0415 (18)	−0.0021 (16)	0.0244 (16)	0.0030 (15)
C13	0.058 (2)	0.050 (2)	0.054 (2)	0.0077 (17)	0.037 (2)	0.0020 (17)
C17	0.104 (4)	0.041 (2)	0.071 (3)	−0.011 (2)	0.062 (3)	−0.0117 (19)
C18	0.068 (3)	0.0407 (19)	0.048 (2)	−0.0059 (17)	0.042 (2)	−0.0054 (15)
C19	0.048 (2)	0.0411 (18)	0.0373 (17)	−0.0111 (15)	0.0294 (17)	−0.0070 (14)
C20	0.057 (2)	0.059 (2)	0.0402 (19)	−0.0170 (18)	0.0275 (19)	−0.0129 (16)
C21	0.081 (3)	0.071 (3)	0.053 (2)	−0.037 (2)	0.037 (2)	−0.029 (2)
C22	0.117 (4)	0.058 (3)	0.073 (3)	−0.036 (3)	0.064 (3)	−0.035 (2)
C31	0.0414 (19)	0.048 (2)	0.0467 (19)	−0.0089 (15)	0.0203 (16)	0.0012 (15)
C32	0.045 (2)	0.047 (2)	0.0433 (19)	−0.0195 (16)	0.0139 (16)	−0.0020 (16)
C33	0.070 (3)	0.048 (2)	0.042 (2)	−0.0191 (19)	0.0139 (18)	0.0026 (16)
C34	0.093 (3)	0.048 (2)	0.062 (3)	−0.021 (2)	0.027 (2)	−0.0026 (19)
C35	0.076 (3)	0.048 (2)	0.074 (3)	−0.021 (2)	0.012 (2)	0.016 (2)
C36	0.078 (3)	0.075 (3)	0.049 (2)	−0.038 (2)	0.002 (2)	0.019 (2)
C37	0.071 (3)	0.064 (3)	0.045 (2)	−0.035 (2)	0.0190 (19)	−0.0010 (18)
C71	0.0340 (17)	0.0324 (16)	0.0402 (17)	−0.0026 (13)	0.0171 (15)	−0.0007 (13)
C72	0.0332 (17)	0.0375 (18)	0.0496 (19)	−0.0026 (13)	0.0157 (15)	−0.0076 (14)
C73	0.044 (2)	0.0388 (19)	0.065 (2)	0.0013 (15)	0.0314 (18)	−0.0082 (16)
C74	0.055 (2)	0.0334 (17)	0.0503 (19)	−0.0015 (15)	0.0269 (17)	−0.0111 (15)
C75	0.047 (2)	0.060 (2)	0.059 (2)	−0.0155 (17)	0.0240 (19)	−0.0261 (18)
C76	0.038 (2)	0.063 (2)	0.062 (2)	−0.0124 (17)	0.0255 (18)	−0.0220 (18)
N1	0.0329 (14)	0.0388 (14)	0.0329 (14)	−0.0056 (11)	0.0122 (12)	0.0006 (11)
N2	0.0421 (15)	0.0365 (14)	0.0362 (14)	−0.0073 (11)	0.0222 (12)	−0.0031 (11)
O1	0.0334 (13)	0.0482 (14)	0.0546 (14)	−0.0037 (11)	0.0171 (11)	−0.0005 (11)
O2	0.0354 (13)	0.0621 (16)	0.0531 (14)	−0.0072 (12)	0.0192 (12)	0.0044 (12)
S1	0.0801 (7)	0.0590 (6)	0.0525 (5)	−0.0222 (5)	0.0396 (5)	0.0010 (4)
Br1	0.0842 (4)	0.0826 (4)	0.0852 (4)	−0.0076 (2)	0.0464 (3)	−0.0444 (2)
C14	0.085 (3)	0.068 (3)	0.077 (3)	0.024 (2)	0.046 (3)	0.006 (2)
C15	0.134 (5)	0.067 (3)	0.115 (4)	0.042 (3)	0.074 (4)	0.008 (3)
C16	0.155 (5)	0.046 (3)	0.110 (4)	0.008 (3)	0.086 (4)	−0.012 (3)
Br2	0.1586 (7)	0.0538 (3)	0.1495 (6)	−0.0125 (3)	0.0172 (5)	0.0345 (3)

Geometric parameters (Å, º)

C1—N1	1.449 (4)	C17—C18	1.410 (5)
C1—H1A	0.9600	C17—C16	1.403 (7)
C1—H1B	0.9600	C18—C19	1.399 (5)
C1—H1C	0.9600	C19—C20	1.363 (5)
C2—N1	1.460 (4)	C20—C21	1.418 (5)
C2—C3	1.501 (4)	C20—H20	0.9300
C2—H2A	0.9700	C21—C22	1.345 (6)
C2—H2B	0.9700	C21—H21	0.9300
C3—C31	1.336 (4)	C22—H22	0.9300
C3—C4	1.478 (4)	C31—C32	1.458 (5)
C4—O1	1.214 (4)	C31—H31	0.9300
C4—C5	1.525 (4)	C32—C33	1.376 (5)
C5—C6	1.532 (4)	C32—C37	1.397 (5)
C5—C7	1.552 (4)	C33—C34	1.372 (5)
C5—C11	1.604 (4)	C33—H33	0.9300
C6—N1	1.442 (4)	C34—C35	1.372 (5)
C6—H6A	0.9700	C34—H34	0.9300
C6—H6B	0.9700	C35—C36	1.367 (6)
C7—C8	1.510 (4)	C35—Br2	1.885 (4)
C7—C71	1.513 (4)	C36—C37	1.369 (6)
C7—H7	0.9800	C36—H36	0.9300
C8—N2	1.455 (4)	C37—H37	0.9300
C8—C9	1.505 (4)	C71—C72	1.381 (4)
C8—H8	0.9800	C71—C76	1.386 (4)
C9—S1	1.818 (3)	C72—C73	1.384 (4)
C9—H9A	0.9700	C72—H72	0.9300
C9—H9B	0.9700	C73—C74	1.362 (5)
C10—N2	1.444 (4)	C73—H73	0.9300
C10—S1	1.821 (3)	C74—C75	1.353 (5)
C10—H10A	0.9700	C74—Br1	1.897 (3)
C10—H10B	0.9700	C75—C76	1.376 (5)
C11—N2	1.462 (4)	C75—H75	0.9300
C11—C19	1.518 (4)	C76—H76	0.9300
C11—C12	1.566 (4)	C14—C15	1.399 (7)
C12—O2	1.214 (4)	C14—H14	0.9300
C12—C13	1.470 (5)	C15—C16	1.363 (7)
C13—C14	1.368 (5)	C15—H15	0.9300
C13—C18	1.390 (5)	C16—H16	0.9300
C17—C22	1.409 (7)
N1—C1—H1A	109.5	C13—C18—C17	122.9 (4)
N1—C1—H1B	109.5	C19—C18—C17	123.7 (4)
H1A—C1—H1B	109.5	C20—C19—C18	118.7 (3)
N1—C1—H1C	109.5	C20—C19—C11	131.8 (3)
H1A—C1—H1C	109.5	C18—C19—C11	109.5 (3)
H1B—C1—H1C	109.5	C19—C20—C21	118.1 (4)
N1—C2—C3	113.4 (2)	C19—C20—H20	120.9
N1—C2—H2A	108.9	C21—C20—H20	120.9
C3—C2—H2A	108.9	C22—C21—C20	123.2 (4)
N1—C2—H2B	108.9	C22—C21—H21	118.4
C3—C2—H2B	108.9	C20—C21—H21	118.4
H2A—C2—H2B	107.7	C21—C22—C17	120.5 (4)
C31—C3—C4	117.7 (3)	C21—C22—H22	119.8
C31—C3—C2	123.2 (3)	C17—C22—H22	119.8
C4—C3—C2	118.9 (3)	C3—C31—C32	127.1 (3)
O1—C4—C3	122.0 (3)	C3—C31—H31	116.5
O1—C4—C5	121.4 (3)	C32—C31—H31	116.5
C3—C4—C5	116.7 (3)	C33—C32—C37	117.5 (3)
C4—C5—C6	106.3 (2)	C33—C32—C31	119.9 (3)
C4—C5—C7	112.7 (2)	C37—C32—C31	122.5 (3)
C6—C5—C7	113.8 (2)	C34—C33—C32	122.5 (3)
C4—C5—C11	110.2 (2)	C34—C33—H33	118.7
C6—C5—C11	109.8 (2)	C32—C33—H33	118.7
C7—C5—C11	104.1 (2)	C35—C34—C33	118.1 (4)
N1—C6—C5	107.6 (2)	C35—C34—H34	121.0
N1—C6—H6A	110.2	C33—C34—H34	121.0
C5—C6—H6A	110.2	C36—C35—C34	121.2 (4)
N1—C6—H6B	110.2	C36—C35—Br2	119.2 (3)
C5—C6—H6B	110.2	C34—C35—Br2	119.5 (3)
H6A—C6—H6B	108.5	C35—C36—C37	120.0 (4)
C8—C7—C71	116.7 (2)	C35—C36—H36	120.0
C8—C7—C5	101.8 (2)	C37—C36—H36	120.0
C71—C7—C5	115.5 (2)	C36—C37—C32	120.4 (4)
C8—C7—H7	107.4	C36—C37—H37	119.8
C71—C7—H7	107.4	C32—C37—H37	119.8
C5—C7—H7	107.4	C72—C71—C76	117.2 (3)
N2—C8—C9	104.2 (2)	C72—C71—C7	120.9 (3)
N2—C8—C7	100.5 (2)	C76—C71—C7	121.9 (3)
C9—C8—C7	119.8 (3)	C73—C72—C71	121.9 (3)
N2—C8—H8	110.5	C73—C72—H72	119.1
C9—C8—H8	110.5	C71—C72—H72	119.1
C7—C8—H8	110.5	C74—C73—C72	118.6 (3)
C8—C9—S1	103.7 (2)	C74—C73—H73	120.7
C8—C9—H9A	111.0	C72—C73—H73	120.7
S1—C9—H9A	111.0	C75—C74—C73	121.3 (3)
C8—C9—H9B	111.0	C75—C74—Br1	119.5 (3)
S1—C9—H9B	111.0	C73—C74—Br1	119.2 (2)
H9A—C9—H9B	109.0	C74—C75—C76	119.9 (3)
N2—C10—S1	104.5 (2)	C74—C75—H75	120.1
N2—C10—H10A	110.8	C76—C75—H75	120.1
S1—C10—H10A	110.8	C75—C76—C71	121.1 (3)
N2—C10—H10B	110.8	C75—C76—H76	119.5
S1—C10—H10B	110.8	C71—C76—H76	119.5
H10A—C10—H10B	108.9	C6—N1—C1	113.9 (2)
N2—C11—C19	112.3 (2)	C6—N1—C2	112.3 (2)
N2—C11—C12	113.3 (2)	C1—N1—C2	111.1 (2)
C19—C11—C12	101.2 (2)	C10—N2—C8	111.5 (2)
N2—C11—C5	101.7 (2)	C10—N2—C11	120.8 (2)
C19—C11—C5	116.8 (2)	C8—N2—C11	107.9 (2)
C12—C11—C5	112.1 (2)	C9—S1—C10	93.49 (14)
O2—C12—C13	127.0 (3)	C13—C14—C15	118.1 (5)
O2—C12—C11	123.8 (3)	C13—C14—H14	121.0
C13—C12—C11	108.4 (3)	C15—C14—H14	121.0
C14—C13—C18	120.0 (4)	C16—C15—C14	122.2 (5)
C14—C13—C12	132.7 (4)	C16—C15—H15	118.9
C18—C13—C12	107.2 (3)	C14—C15—H15	118.9
C22—C17—C18	115.7 (4)	C15—C16—C17	121.3 (4)
C22—C17—C16	128.8 (4)	C15—C16—H16	119.3
C18—C17—C16	115.5 (4)	C17—C16—H16	119.3
C13—C18—C19	113.4 (3)
N1—C2—C3—C31	−151.8 (3)	N2—C11—C19—C18	−126.9 (3)
N1—C2—C3—C4	24.0 (4)	C12—C11—C19—C18	−5.7 (3)
C31—C3—C4—O1	−27.1 (4)	C5—C11—C19—C18	116.2 (3)
C2—C3—C4—O1	156.9 (3)	C18—C19—C20—C21	−2.7 (4)
C31—C3—C4—C5	151.5 (3)	C11—C19—C20—C21	178.2 (3)
C2—C3—C4—C5	−24.5 (4)	C19—C20—C21—C22	1.2 (5)
O1—C4—C5—C6	−137.9 (3)	C20—C21—C22—C17	0.3 (6)
C3—C4—C5—C6	43.6 (3)	C18—C17—C22—C21	−0.2 (5)
O1—C4—C5—C7	−12.6 (4)	C16—C17—C22—C21	177.0 (4)
C3—C4—C5—C7	168.9 (2)	C4—C3—C31—C32	−172.3 (3)
O1—C4—C5—C11	103.2 (3)	C2—C3—C31—C32	3.5 (5)
C3—C4—C5—C11	−75.4 (3)	C3—C31—C32—C33	133.3 (4)
C4—C5—C6—N1	−65.5 (3)	C3—C31—C32—C37	−44.0 (5)
C7—C5—C6—N1	169.8 (2)	C37—C32—C33—C34	5.8 (6)
C11—C5—C6—N1	53.7 (3)	C31—C32—C33—C34	−171.7 (4)
C4—C5—C7—C8	146.3 (2)	C32—C33—C34—C35	−2.3 (6)
C6—C5—C7—C8	−92.6 (3)	C33—C34—C35—C36	−2.4 (7)
C11—C5—C7—C8	26.9 (3)	C33—C34—C35—Br2	177.1 (3)
C4—C5—C7—C71	−86.2 (3)	C34—C35—C36—C37	3.5 (7)
C6—C5—C7—C71	34.9 (3)	Br2—C35—C36—C37	−176.1 (3)
C11—C5—C7—C71	154.4 (2)	C35—C36—C37—C32	0.2 (6)
C71—C7—C8—N2	−171.8 (2)	C33—C32—C37—C36	−4.6 (6)
C5—C7—C8—N2	−45.1 (3)	C31—C32—C37—C36	172.7 (4)
C71—C7—C8—C9	75.0 (4)	C8—C7—C71—C72	−151.2 (3)
C5—C7—C8—C9	−158.3 (3)	C5—C7—C71—C72	89.2 (3)
N2—C8—C9—S1	43.0 (3)	C8—C7—C71—C76	27.6 (4)
C7—C8—C9—S1	154.2 (2)	C5—C7—C71—C76	−92.0 (4)
C4—C5—C11—N2	−120.1 (2)	C76—C71—C72—C73	2.4 (5)
C6—C5—C11—N2	123.1 (2)	C7—C71—C72—C73	−178.8 (3)
C7—C5—C11—N2	1.0 (3)	C71—C72—C73—C74	−0.5 (5)
C4—C5—C11—C19	2.5 (4)	C72—C73—C74—C75	−1.8 (5)
C6—C5—C11—C19	−114.3 (3)	C72—C73—C74—Br1	178.0 (2)
C7—C5—C11—C19	123.6 (3)	C73—C74—C75—C76	2.1 (6)
C4—C5—C11—C12	118.5 (3)	Br1—C74—C75—C76	−177.7 (3)
C6—C5—C11—C12	1.8 (3)	C74—C75—C76—C71	−0.1 (6)
C7—C5—C11—C12	−120.3 (3)	C72—C71—C76—C75	−2.1 (5)
N2—C11—C12—O2	−44.4 (4)	C7—C71—C76—C75	179.1 (3)
C19—C11—C12—O2	−164.8 (3)	C5—C6—N1—C1	−162.5 (2)
C5—C11—C12—O2	70.1 (4)	C5—C6—N1—C2	70.1 (3)
N2—C11—C12—C13	126.0 (3)	C3—C2—N1—C6	−47.1 (3)
C19—C11—C12—C13	5.5 (3)	C3—C2—N1—C1	−176.0 (3)
C5—C11—C12—C13	−119.6 (3)	S1—C10—N2—C8	33.1 (3)
O2—C12—C13—C14	−11.4 (6)	S1—C10—N2—C11	161.4 (2)
C11—C12—C13—C14	178.7 (4)	C9—C8—N2—C10	−51.4 (3)
O2—C12—C13—C18	166.4 (3)	C7—C8—N2—C10	−176.0 (2)
C11—C12—C13—C18	−3.5 (3)	C9—C8—N2—C11	173.8 (2)
C14—C13—C18—C19	177.8 (3)	C7—C8—N2—C11	49.1 (3)
C12—C13—C18—C19	−0.3 (4)	C19—C11—N2—C10	73.9 (3)
C14—C13—C18—C17	−0.3 (5)	C12—C11—N2—C10	−40.0 (4)
C12—C13—C18—C17	−178.5 (3)	C5—C11—N2—C10	−160.5 (2)
C22—C17—C18—C13	176.5 (3)	C19—C11—N2—C8	−156.3 (2)
C16—C17—C18—C13	−1.0 (5)	C12—C11—N2—C8	89.8 (3)
C22—C17—C18—C19	−1.5 (5)	C5—C11—N2—C8	−30.7 (3)
C16—C17—C18—C19	−179.0 (3)	C8—C9—S1—C10	−22.1 (2)
C13—C18—C19—C20	−175.1 (3)	N2—C10—S1—C9	−4.9 (2)
C17—C18—C19—C20	3.0 (5)	C18—C13—C14—C15	1.2 (6)
C13—C18—C19—C11	4.1 (4)	C12—C13—C14—C15	178.8 (4)
C17—C18—C19—C11	−177.7 (3)	C13—C14—C15—C16	−0.7 (7)
N2—C11—C19—C20	52.3 (4)	C14—C15—C16—C17	−0.7 (8)
C12—C11—C19—C20	173.4 (3)	C22—C17—C16—C15	−175.6 (5)
C5—C11—C19—C20	−64.7 (4)	C18—C17—C16—C15	1.6 (7)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of WHICH? ring.

D—H···A	D—H	H···A	D···A	D—H···A
C34—H34···O1^i	0.93	2.57	3.440 (5)	157
C76—H76···O2^ii	0.93	2.46	3.250 (5)	143
C73—H73···O1^iii	0.93	2.45	3.361 (5)	166
C9—H9B···O2^ii	0.97	2.62	3.298 (3)	128
C10—H10A···O2	0.97	2.54	3.176 (4)	123
C2—H2B···Cg1^iv	0.97	2.90	3.816 (3)	159

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