7-Chloro-1-(2,6-di­fluoro­phenyl)-1H,3H-thia­zolo­[3,4-a]­benz­imidazole and 1-(2,6-di­fluoro­phenyl)-6-methyl-1H,3H-thia­zolo­[3,4-a]­benz­imidazole

The title mol­ecules, C₁₅H₉ClF₂N₂S and C₁₆H₁₂F₂N₂S, respectively, display the well known butterfly-like conformation with a flat thia­zolobenz­imidazole system. In both compounds, the mean plane through the tricyclic system is almost perpendicular to the 2,6-di­fluoro­phenyl ring. This arrangement of the aryl group is determined by two intramolecular hydrogen bonds and by an attractive F...S interaction.

S1. Comment

As part of a structure–activity relationship study on a series of thiazolo[3,4-a]benzimidazole derivatives endowed with anti-HIV activity, we have already demonstrated (Chimirri et al., 1997) that the geometric features of 1-(2,6-difluorophenyl)-1H,3H-thiazolo[3,4-a]benzimidazole (TBZ), the lead compound of the series, determine the biological activity. Moreover, we have observed (Chimirri et al., 1996) that the anti-HIV activity is maintained by introducing a Cl atom at position 7 of the tricyclic system, whereas the presence of a methyl group at position 6 leads to a drop-off in activity. In this context, we report the crystal structures of 7-chloro-1-(2,6-difluorophenyl)-1H,3H-thiazolo[3,4-a]benzimidazole, (I), and 1-(2,6-difluorophenyl)-6-methyl-1H,3H-thiazolo[3,4-a]benzimidazole, (II), in order to determine whether the difference in activity could be related to any change in the molecular geometry or to the presence of a substituent on the benzene ring.

Both compounds (I) and (II) are built up by three fused rings to form a flat thiazolobenzimidazole system (the atomic deviations from the weighted least-squares mean plane are within 0.02 Å); the thiazole ring in (I) has a chiral C atom bonding the 2,6-difluorophenyl group. Since both compounds crystallize in centrosymmetric space groups, in the solid state, a racemic mixture is obtained from the synthesis. The molecular structure determinations of (I) and (II) confirm the well known butterfly conformation, already shown to exist in other 1-aryl-1H,3H-thiazolo[3,4-a]benzimidazole derivatives (Bruno et al., 1996, 1997, 1998). Such a disposition is evidenced by considering the dihedral angle between the three fused rings (the thiazolobenzimidazole system) and the 2,6-difluorophenyl substituent at C1, i.e. 100.28 (5) and 87.62 (6)° for (I) and 2, respectively. This arrangement is mainly due either to hindered rotation around the C1—C10 bond axis or to further stabilization through an intramolecular interaction between the H atom of the chiral Csp³ atom and the electron-rich F atoms [F1···C1 = 2.793 (2) Å and C1—H1···F1 = 108.2 (1)°, and F2···C9 = 2.990 (2) Å and F2···H9—C9 108.8 (2)° for (I); F2···C1 = 2.781 (3) Å and C1—H1···F2 = 108.6 (2)°, and F1···C9 = 3.225 (2) Å and F1···H9B—C9 97.6 (2)° for (II)].

However, the puckering analysis (Cremer & People, 1975) shows that the conformations of five-membered thiazolidine ring (S/C9/C8/N2/C1) are essentially different in (I) and (II); the conformation is intermediate between envelope (ϕ = 180°) and twisted (ϕ = 90°) in (I) [ϕ = -145.4 (4)°, Q = 0.221 (2) and Dσ(S) = 0.005 (1)] and a flatter envelope in (II) [ϕ = -170 (1)°, Q = 0.097 (2) and D2(C8) = 0.006 (1)]. Such a difference may arise from the attractive F1···S [3.063 (1) Å] interaction (Bruno, Nicoló et al., 1997) that in (I) pushes the S atom up to -0.398 (1) Å out of the best mean plane through atoms C9/C8/N2/C1 on the opposite side of the F atom. In (II), the larger F···S separation of 3.236 (2) Å leaves the S atom 0.179 (1) Å out of this plane.

Bond distances of the thiazolidine ring are similar to those observed in a series of analogous TBZ compounds. In each compound, the bond distances involving the S atom, S—C1 and S—C9, are not equivalent: 1.838 (2) and 1.825 (2) Å in (I) versus 1.848 (2) and 1.816 (2) Å in (II). The significant difference of 0.032 Å in (II) might be caused by the steric effect of the 2,6-difluorophenyl group linked to the C1 atom. The endocyclic C9—S—C1 bond angles of 95.3 (1) and 95.4 (1)° for (I) and (II), respectively, are in the narrow range of values reported in the Cambridge Structural Database (Allen et al., 1991) for penicillin and other biologically active substituted thiazolidines. The sum of the valence angles around N2 is 360.0 (1)° in (I) and 359.8 (2)° in (II), indicating its sp² hybridization. The N—C bond distances are also indicative of the π-delocalization over the whole naphthoimidazole fragment.

The molecular packing for both compounds is essentially determined by normal van der Waals interactions and some weak hydrogen bonds involving the F and N atoms as acceptors. However, the H···N intermolecular network in compound (I) causes each centrosymmetric molecular pair to assume a flat head-to-tail disposition. Each couple acts as a step of a staircase constituted by their overlap along the b axis like a pseudo-polymeric column, as shown in Fig. 3.

Related literature

For related literature, see: Allen et al. (1991); Bruno et al. (1996, 1998); Bruno, Chimirri, Monforte, Nicoló & Scopelliti (1997); Bruno, Nicoló, Chimirri, Grasso, Monforte, Monforte, Zappalá, Rao & Scopelliti (1997); Chimirri et al. (1996, 1997).

S2. Experimental

The title compounds were obtained as described previously by Chimirri et al. (1996). Suitable single crystals were obtained by recrystallization from ethanol.

S3. Refinement

H atoms were placed in calculated positions (the idealized geometry depending on the parent atom type) and included in the refinement as riding atoms, with a common fixed isotropic displacement parameter (U_iso = 0.06 Ų). The usual rotational disorder of the terminal methyl group in compound (II) was handled by splitting it into two staggered positions, and fixing their occupancies to the best values (0.6 versus 0.4).

Computing details

For both compounds, data collection: P3/V (Siemens, 1989); cell refinement: P3/V; data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: locally modified PARST97 (Nardelli, 1995) and SHELXL97.

Figures

	Fig. 1. Perspective view of (I) showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. Perspective view of (II) showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 3. The crystal packing of compound (I) showing the intermolecular hydrogen-bond interactions as dotted lines. Atom size is arbitrary. Cross-hatched circles indicate N atoms.

(I) 7-chloro-1-(2,6-difluorophenyl)-1H,3H-thiazolo[3,4-a]benzimidazole

Crystal data

C15H9ClF2N2S	F(000) = 656
Mr = 322.75	Dx = 1.552 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.292 (2) Å	Cell parameters from 30 reflections
b = 5.741 (1) Å	θ = 6.3–14.9°
c = 23.474 (4) Å	µ = 0.44 mm^−1
β = 95.05 (1)°	T = 293 K
V = 1381.6 (4) Å^3	Prism, colourless
Z = 4	0.34 × 0.23 × 0.17 mm

Data collection

Siemens P4 diffractometer	Rint = 0.013
Radiation source: fine-focus sealed tube	θmax = 26.1°, θmin = 1.7°
Graphite monochromator	h = −5→12
ω–2θ scans	k = −3→7
3993 measured reflections	l = −29→29
2720 independent reflections	3 standard reflections every 197 reflections
2170 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0452P)^2 + 0.3215P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2720 reflections	Δρmax = 0.20 e Å^−3
191 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0041 (11)

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. Reflection intensities were evaluated by profile fitting of a 96-step peak scan among 2θ shells (Diamond, 1969). Whereas the final difference Fourier maps showed several H-atom positions.

Diamond, R. (1969). Acta Cryst. A25, 43–55.

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S	0.77120 (4)	0.20390 (10)	0.36066 (2)	0.05641 (18)	(I)
C1	0.59458 (15)	0.2581 (3)	0.35513 (7)	0.0367 (4)	(I)
H1	0.5788	0.4087	0.3729	0.060*	(I)
N2	0.54823 (12)	0.0747 (2)	0.39076 (5)	0.0340 (3)	(I)
C8	0.62711 (16)	−0.1072 (3)	0.40779 (7)	0.0381 (4)	(I)
C9	0.76023 (17)	−0.0928 (4)	0.38772 (8)	0.0503 (5)	(I)
H9A	0.7707	−0.2056	0.3577	0.060*	(I)
H9B	0.8265	−0.1207	0.4190	0.060*	(I)
C2	0.43027 (14)	0.0379 (3)	0.41299 (6)	0.0321 (3)	(I)
C7	0.44740 (16)	−0.1742 (3)	0.44275 (6)	0.0357 (4)	(I)
N1	0.57304 (14)	−0.2620 (2)	0.43858 (6)	0.0410 (3)	(I)
C3	0.31737 (15)	0.1695 (3)	0.41126 (6)	0.0367 (4)	(I)
H3	0.3078	0.3097	0.3915	0.060*	(I)
C4	0.21987 (16)	0.0767 (3)	0.44122 (7)	0.0408 (4)	(I)
Cl	0.07486 (5)	0.23378 (11)	0.44232 (2)	0.06610 (19)	(I)
C5	0.23216 (17)	−0.1342 (3)	0.47046 (7)	0.0448 (4)	(I)
H5	0.1625	−0.1900	0.4891	0.060*	(I)
C6	0.34588 (18)	−0.2614 (3)	0.47220 (7)	0.0430 (4)	(I)
H6	0.3547	−0.4008	0.4923	0.060*	(I)
C10	0.52532 (16)	0.2557 (3)	0.29540 (7)	0.0377 (4)	(I)
C11	0.53815 (19)	0.0806 (4)	0.25598 (7)	0.0493 (5)	(I)
F1	0.61742 (13)	−0.1004 (2)	0.27117 (5)	0.0717 (4)	(I)
C12	0.4723 (2)	0.0788 (4)	0.20216 (8)	0.0626 (6)	(I)
H12	0.4839	−0.0423	0.1768	0.060*	(I)
C13	0.3896 (2)	0.2595 (4)	0.18694 (8)	0.0656 (6)	(I)
H13	0.3449	0.2613	0.1507	0.060*	(I)
C14	0.3716 (2)	0.4380 (4)	0.22432 (8)	0.0620 (6)	(I)
H14	0.3149	0.5600	0.2140	0.060*	(I)
C15	0.43971 (18)	0.4317 (3)	0.27741 (7)	0.0469 (4)	(I)
F2	0.41965 (13)	0.6049 (2)	0.31481 (5)	0.0669 (4)	(I)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0339 (2)	0.0676 (4)	0.0677 (3)	−0.0055 (2)	0.0040 (2)	0.0146 (3)
C1	0.0354 (8)	0.0391 (9)	0.0358 (8)	−0.0039 (7)	0.0036 (6)	0.0025 (7)
N2	0.0356 (7)	0.0363 (7)	0.0301 (6)	−0.0008 (6)	0.0026 (5)	0.0032 (5)
C8	0.0408 (8)	0.0402 (9)	0.0325 (8)	0.0035 (7)	−0.0013 (6)	−0.0021 (7)
C9	0.0409 (9)	0.0574 (12)	0.0524 (10)	0.0085 (9)	0.0027 (8)	0.0041 (9)
C2	0.0360 (8)	0.0373 (8)	0.0226 (6)	−0.0057 (7)	0.0003 (6)	−0.0005 (6)
C7	0.0447 (9)	0.0361 (8)	0.0257 (7)	−0.0034 (7)	−0.0007 (6)	−0.0020 (6)
N1	0.0488 (8)	0.0381 (8)	0.0354 (7)	0.0026 (6)	−0.0010 (6)	0.0015 (6)
C3	0.0375 (8)	0.0432 (9)	0.0289 (7)	−0.0033 (7)	−0.0007 (6)	0.0016 (7)
C4	0.0354 (8)	0.0547 (11)	0.0322 (8)	−0.0023 (8)	0.0022 (6)	−0.0021 (8)
Cl	0.0400 (3)	0.0878 (4)	0.0725 (4)	0.0091 (2)	0.0157 (2)	0.0161 (3)
C5	0.0471 (10)	0.0548 (11)	0.0332 (8)	−0.0138 (9)	0.0067 (7)	0.0010 (8)
C6	0.0577 (11)	0.0413 (9)	0.0300 (8)	−0.0108 (8)	0.0033 (7)	0.0040 (7)
C10	0.0395 (8)	0.0434 (9)	0.0310 (8)	−0.0035 (7)	0.0076 (6)	0.0051 (7)
C11	0.0536 (10)	0.0577 (12)	0.0368 (9)	0.0067 (9)	0.0058 (8)	0.0011 (8)
F1	0.0870 (9)	0.0710 (8)	0.0557 (7)	0.0301 (7)	−0.0024 (6)	−0.0134 (6)
C12	0.0755 (14)	0.0783 (15)	0.0342 (9)	0.0015 (12)	0.0056 (9)	−0.0099 (10)
C13	0.0741 (14)	0.0868 (16)	0.0337 (9)	−0.0020 (13)	−0.0075 (9)	0.0075 (11)
C14	0.0692 (13)	0.0664 (14)	0.0477 (10)	0.0096 (11)	−0.0097 (9)	0.0130 (10)
C15	0.0531 (10)	0.0477 (11)	0.0397 (9)	−0.0003 (9)	0.0025 (8)	0.0040 (8)
F2	0.0817 (8)	0.0555 (7)	0.0607 (7)	0.0221 (6)	−0.0096 (6)	−0.0068 (6)

Geometric parameters (Å, º)

S—C9	1.825 (2)	C3—C4	1.382 (2)
S—C1	1.8375 (17)	C4—C5	1.392 (3)
C1—N2	1.451 (2)	C4—Cl	1.7459 (18)
C1—C10	1.516 (2)	C5—C6	1.377 (3)
N2—C8	1.361 (2)	C10—C11	1.381 (2)
N2—C2	1.3792 (19)	C10—C15	1.382 (2)
C8—N1	1.301 (2)	C11—F1	1.349 (2)
C8—C9	1.490 (2)	C11—C12	1.380 (3)
C2—C3	1.384 (2)	C12—C13	1.369 (3)
C2—C7	1.407 (2)	C13—C14	1.372 (3)
C7—C6	1.396 (2)	C14—C15	1.375 (3)
C7—N1	1.399 (2)	C15—F2	1.354 (2)
C9—S—C1	95.25 (8)	C4—C3—C2	114.84 (15)
N2—C1—C10	112.02 (13)	C3—C4—C5	123.22 (16)
N2—C1—S	102.11 (11)	C3—C4—Cl	117.92 (14)
C10—C1—S	116.46 (12)	C5—C4—Cl	118.86 (13)
C8—N2—C2	107.06 (13)	C6—C5—C4	121.06 (16)
C8—N2—C1	120.54 (13)	C5—C6—C7	117.81 (16)
C2—N2—C1	132.39 (14)	C11—C10—C15	115.06 (16)
N1—C8—N2	114.46 (15)	C11—C10—C1	124.15 (16)
N1—C8—C9	131.60 (16)	C15—C10—C1	120.75 (15)
N2—C8—C9	113.94 (15)	F1—C11—C12	118.24 (18)
C8—C9—S	104.41 (12)	F1—C11—C10	118.35 (15)
N2—C2—C3	132.08 (15)	C12—C11—C10	123.40 (19)
N2—C2—C7	104.15 (13)	C13—C12—C11	118.5 (2)
C3—C2—C7	123.73 (14)	C12—C13—C14	120.97 (18)
C6—C7—N1	129.95 (16)	C13—C14—C15	118.2 (2)
C6—C7—C2	119.33 (15)	F2—C15—C14	118.25 (18)
N1—C7—C2	110.69 (14)	F2—C15—C10	117.91 (15)
C8—N1—C7	103.64 (14)	C14—C15—C10	123.82 (18)
C9—S—C1—N2	17.12 (12)	C7—C2—C3—C4	−0.2 (2)
C9—S—C1—C10	−105.23 (14)	C2—C3—C4—C5	−0.8 (2)
C10—C1—N2—C8	111.60 (16)	C2—C3—C4—Cl	178.97 (11)
S—C1—N2—C8	−13.74 (17)	C3—C4—C5—C6	1.6 (3)
C10—C1—N2—C2	−67.5 (2)	Cl—C4—C5—C6	−178.20 (13)
S—C1—N2—C2	167.18 (14)	C4—C5—C6—C7	−1.2 (2)
C2—N2—C8—N1	0.63 (18)	N1—C7—C6—C5	177.97 (15)
C1—N2—C8—N1	−178.66 (14)	C2—C7—C6—C5	0.2 (2)
C2—N2—C8—C9	−179.34 (14)	N2—C1—C10—C11	−67.2 (2)
C1—N2—C8—C9	1.4 (2)	S—C1—C10—C11	49.8 (2)
N1—C8—C9—S	−167.96 (16)	N2—C1—C10—C15	110.71 (18)
N2—C8—C9—S	12.01 (18)	S—C1—C10—C15	−132.29 (15)
C1—S—C9—C8	−16.96 (13)	C15—C10—C11—F1	−178.22 (17)
C8—N2—C2—C3	177.12 (16)	C1—C10—C11—F1	−0.2 (3)
C1—N2—C2—C3	−3.7 (3)	C15—C10—C11—C12	0.6 (3)
C8—N2—C2—C7	−0.46 (16)	C1—C10—C11—C12	178.65 (18)
C1—N2—C2—C7	178.72 (15)	F1—C11—C12—C13	178.6 (2)
N2—C2—C7—C6	178.32 (14)	C10—C11—C12—C13	−0.2 (3)
C3—C2—C7—C6	0.5 (2)	C11—C12—C13—C14	−0.4 (3)
N2—C2—C7—N1	0.19 (16)	C12—C13—C14—C15	0.5 (3)
C3—C2—C7—N1	−177.65 (14)	C13—C14—C15—F2	−178.44 (19)
N2—C8—N1—C7	−0.49 (18)	C13—C14—C15—C10	0.0 (3)
C9—C8—N1—C7	179.48 (18)	C11—C10—C15—F2	177.92 (16)
C6—C7—N1—C8	−177.71 (16)	C1—C10—C15—F2	−0.2 (2)
C2—C7—N1—C8	0.17 (17)	C11—C10—C15—C14	−0.5 (3)
N2—C2—C3—C4	−177.38 (15)	C1—C10—C15—C14	−178.60 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F2	0.98	2.33	2.793 (2)	108
C9—H9A···F1	0.97	2.53	2.990 (2)	109
C1—H1···N1^i	0.98	2.44	3.399 (2)	165
C6—H6···N1^ii	0.93	2.59	3.502 (2)	166

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

(2) 1-(2,6-Difluorophenyl)-6-methyl-1H,3H-thiazolo[3,4-a]benzimidazole

Crystal data

C16H12F2N2S	Z = 2
Mr = 302.34	F(000) = 312
Triclinic, P1	Dx = 1.432 Mg m^−3
a = 7.616 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.202 (3) Å	Cell parameters from 40 reflections
c = 10.868 (2) Å	θ = 7.2–15.8°
α = 108.86 (2)°	µ = 0.25 mm^−1
β = 106.96 (1)°	T = 293 K
γ = 105.46 (2)°	Irregular, colourless
V = 701.0 (3) Å^3	0.30 × 0.28 × 0.26 mm

Data collection

Siemens P4 diffractometer	Rint = 0.011
Radiation source: fine-focus sealed tube	θmax = 24.6°, θmin = 2.2°
Graphite monochromator	h = −4→8
ω–2θ scans	k = −11→11
3013 measured reflections	l = −12→12
2342 independent reflections	3 standard reflections every 197 reflections
1713 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0427P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max < 0.001
2342 reflections	Δρmax = 0.18 e Å^−3
192 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (2)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S	0.31356 (8)	0.52479 (6)	0.84683 (5)	0.05986 (18)	(I)
C1	0.5261 (2)	0.58103 (18)	0.79877 (16)	0.0411 (4)	(I)
H1	0.5488	0.4912	0.7526	0.060*	(I)
N2	0.4518 (2)	0.63423 (14)	0.69366 (13)	0.0398 (3)	(I)
C8	0.2744 (3)	0.64877 (19)	0.66695 (17)	0.0457 (4)	(I)
C9	0.1658 (3)	0.6001 (2)	0.7481 (2)	0.0602 (5)	(I)
H9A	0.0327	0.5232	0.6835	0.060*	(I)
H9B	0.1539	0.6851	0.8129	0.060*	(I)
C2	0.5359 (2)	0.68733 (16)	0.61320 (15)	0.0385 (4)	(I)
C7	0.3954 (3)	0.73205 (18)	0.54034 (17)	0.0443 (4)	(I)
N1	0.2310 (2)	0.70559 (17)	0.57567 (15)	0.0540 (4)	(I)
C3	0.7104 (3)	0.69867 (18)	0.59514 (16)	0.0440 (4)	(I)
H3	0.8006	0.6664	0.6421	0.060*	(I)
C4	0.7451 (3)	0.76006 (19)	0.50412 (17)	0.0517 (5)	(I)
H4	0.8619	0.7695	0.4903	0.060*	(I)
C5	0.6111 (3)	0.8086 (2)	0.43187 (18)	0.0534 (5)	(I)
C16	0.6587 (4)	0.8741 (3)	0.3332 (2)	0.0782 (7)	(I)
H16A	0.5762	0.9279	0.3138	0.060*	0.60
H16B	0.6331	0.7939	0.2452	0.060*	0.60
H16C	0.7971	0.9421	0.3779	0.060*	0.60
H16D	0.7614	0.8481	0.3108	0.060*	0.40
H16E	0.7045	0.9821	0.3794	0.060*	0.40
H16F	0.5405	0.8339	0.2468	0.060*	0.40
C6	0.4349 (3)	0.7931 (2)	0.44925 (18)	0.0552 (5)	(I)
H6	0.3437	0.8233	0.4003	0.060*	(I)
C10	0.7174 (2)	0.69752 (17)	0.92362 (15)	0.0374 (4)	(I)
C11	0.7434 (3)	0.8425 (2)	1.00688 (18)	0.0497 (5)	(I)
F1	0.58454 (18)	0.88086 (13)	0.97266 (12)	0.0787 (4)	(I)
C12	0.9178 (3)	0.9474 (2)	1.12085 (18)	0.0599 (5)	(I)
H12	0.9274	1.0431	1.1740	0.060*	(I)
C13	1.0780 (3)	0.9086 (2)	1.15499 (19)	0.0603 (5)	(I)
H13	1.1977	0.9786	1.2322	0.060*	(I)
C14	1.0641 (3)	0.7668 (2)	1.07622 (18)	0.0545 (5)	(I)
H14	1.1730	0.7402	1.0985	0.060*	(I)
C15	0.8848 (3)	0.66622 (18)	0.96401 (16)	0.0418 (4)	(I)
F2	0.86969 (16)	0.52610 (11)	0.88627 (11)	0.0591 (3)	(I)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0525 (3)	0.0715 (3)	0.0656 (3)	0.0201 (3)	0.0280 (3)	0.0419 (3)
C1	0.0422 (10)	0.0406 (9)	0.0398 (8)	0.0159 (8)	0.0148 (8)	0.0189 (7)
N2	0.0374 (8)	0.0436 (8)	0.0367 (7)	0.0160 (7)	0.0120 (6)	0.0187 (6)
C8	0.0358 (10)	0.0513 (10)	0.0446 (9)	0.0164 (8)	0.0125 (8)	0.0193 (8)
C9	0.0414 (11)	0.0764 (13)	0.0647 (12)	0.0213 (10)	0.0225 (10)	0.0343 (11)
C2	0.0394 (10)	0.0334 (9)	0.0322 (8)	0.0108 (8)	0.0092 (7)	0.0101 (7)
C7	0.0424 (10)	0.0433 (9)	0.0395 (9)	0.0150 (8)	0.0106 (8)	0.0165 (8)
N1	0.0448 (9)	0.0654 (10)	0.0555 (9)	0.0259 (8)	0.0153 (8)	0.0324 (8)
C3	0.0419 (10)	0.0428 (9)	0.0374 (9)	0.0136 (8)	0.0126 (8)	0.0121 (8)
C4	0.0503 (11)	0.0479 (10)	0.0418 (9)	0.0095 (9)	0.0198 (9)	0.0098 (8)
C5	0.0654 (13)	0.0440 (10)	0.0409 (9)	0.0128 (10)	0.0203 (9)	0.0159 (8)
C16	0.1003 (18)	0.0746 (14)	0.0703 (13)	0.0293 (13)	0.0434 (13)	0.0411 (12)
C6	0.0629 (13)	0.0517 (11)	0.0461 (10)	0.0226 (10)	0.0128 (10)	0.0248 (9)
C10	0.0417 (10)	0.0385 (9)	0.0320 (8)	0.0148 (8)	0.0145 (7)	0.0170 (7)
C11	0.0574 (12)	0.0478 (10)	0.0444 (9)	0.0267 (10)	0.0174 (9)	0.0193 (9)
F1	0.0765 (8)	0.0642 (7)	0.0786 (8)	0.0443 (7)	0.0159 (7)	0.0129 (6)
C12	0.0727 (15)	0.0419 (11)	0.0451 (10)	0.0169 (11)	0.0136 (11)	0.0099 (9)
C13	0.0558 (13)	0.0545 (12)	0.0419 (10)	0.0066 (10)	0.0034 (9)	0.0153 (9)
C14	0.0430 (11)	0.0615 (12)	0.0508 (10)	0.0178 (10)	0.0092 (9)	0.0262 (10)
C15	0.0491 (11)	0.0397 (10)	0.0382 (9)	0.0177 (8)	0.0177 (8)	0.0190 (8)
F2	0.0581 (7)	0.0506 (6)	0.0622 (6)	0.0293 (5)	0.0167 (5)	0.0184 (5)

Geometric parameters (Å, º)

S—C9	1.8162 (19)	C3—C4	1.380 (2)
S—C1	1.8475 (18)	C4—C5	1.399 (3)
C1—N2	1.452 (2)	C5—C6	1.384 (3)
C1—C10	1.502 (2)	C5—C16	1.513 (3)
N2—C8	1.355 (2)	C10—C15	1.379 (2)
N2—C2	1.384 (2)	C10—C11	1.386 (2)
C8—N1	1.309 (2)	C11—F1	1.356 (2)
C8—C9	1.482 (2)	C11—C12	1.367 (3)
C2—C3	1.380 (2)	C12—C13	1.368 (3)
C2—C7	1.407 (2)	C13—C14	1.379 (3)
C7—C6	1.389 (3)	C14—C15	1.370 (2)
C7—N1	1.399 (2)	C15—F2	1.3585 (19)
C9—S—C1	95.38 (8)	C2—C3—C4	116.93 (17)
N2—C1—C10	112.95 (13)	C3—C4—C5	122.48 (18)
N2—C1—S	102.96 (11)	C6—C5—C4	119.55 (17)
C10—C1—S	113.93 (11)	C6—C5—C16	120.94 (19)
C8—N2—C2	107.32 (13)	C4—C5—C16	119.49 (19)
C8—N2—C1	120.61 (14)	C5—C6—C7	119.50 (18)
C2—N2—C1	131.91 (14)	C15—C10—C11	114.31 (15)
N1—C8—N2	114.16 (16)	C15—C10—C1	121.23 (15)
N1—C8—C9	131.41 (17)	C11—C10—C1	124.46 (16)
N2—C8—C9	114.41 (15)	F1—C11—C12	118.67 (17)
C8—C9—S	105.89 (13)	F1—C11—C10	117.33 (16)
C3—C2—N2	133.57 (15)	C12—C11—C10	124.00 (18)
C3—C2—C7	122.32 (16)	C11—C12—C13	118.56 (18)
N2—C2—C7	104.09 (15)	C12—C13—C14	120.79 (18)
C6—C7—N1	130.20 (17)	C15—C14—C13	117.88 (18)
C6—C7—C2	119.19 (17)	F2—C15—C14	118.22 (16)
N1—C7—C2	110.61 (15)	F2—C15—C10	117.32 (15)
C8—N1—C7	103.81 (14)	C14—C15—C10	124.46 (16)
C9—S—C1—N2	−7.82 (12)	C7—C2—C3—C4	1.6 (2)
C9—S—C1—C10	114.86 (13)	C2—C3—C4—C5	−0.3 (2)
C10—C1—N2—C8	−115.96 (17)	C3—C4—C5—C6	−1.1 (3)
S—C1—N2—C8	7.37 (17)	C3—C4—C5—C16	−179.71 (15)
C10—C1—N2—C2	58.9 (2)	C4—C5—C6—C7	1.2 (3)
S—C1—N2—C2	−177.73 (13)	C16—C5—C6—C7	179.79 (15)
C2—N2—C8—N1	0.4 (2)	N1—C7—C6—C5	179.77 (17)
C1—N2—C8—N1	176.44 (14)	C2—C7—C6—C5	0.0 (3)
C2—N2—C8—C9	−178.56 (14)	N2—C1—C10—C15	−125.79 (16)
C1—N2—C8—C9	−2.5 (2)	S—C1—C10—C15	117.18 (15)
N1—C8—C9—S	177.33 (17)	N2—C1—C10—C11	54.0 (2)
N2—C8—C9—S	−3.92 (19)	S—C1—C10—C11	−63.06 (19)
C1—S—C9—C8	6.89 (14)	C15—C10—C11—F1	179.85 (15)
C8—N2—C2—C3	−178.92 (17)	C1—C10—C11—F1	0.1 (2)
C1—N2—C2—C3	5.7 (3)	C15—C10—C11—C12	−0.6 (3)
C8—N2—C2—C7	−0.03 (16)	C1—C10—C11—C12	179.58 (17)
C1—N2—C2—C7	−175.43 (15)	F1—C11—C12—C13	−179.87 (17)
C3—C2—C7—C6	−1.5 (2)	C10—C11—C12—C13	0.6 (3)
N2—C2—C7—C6	179.45 (14)	C11—C12—C13—C14	0.0 (3)
C3—C2—C7—N1	178.72 (15)	C12—C13—C14—C15	−0.6 (3)
N2—C2—C7—N1	−0.32 (17)	C13—C14—C15—F2	−179.73 (16)
N2—C8—N1—C7	−0.6 (2)	C13—C14—C15—C10	0.6 (3)
C9—C8—N1—C7	178.17 (18)	C11—C10—C15—F2	−179.67 (14)
C6—C7—N1—C8	−179.19 (17)	C1—C10—C15—F2	0.1 (2)
C2—C7—N1—C8	0.56 (19)	C11—C10—C15—C14	0.0 (2)
N2—C2—C3—C4	−179.68 (15)	C1—C10—C15—C14	179.82 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F2	0.98	2.31	2.782 (2)	109
C9—H9B···F1	0.97	2.95	3.225 (3)	98