Anomeric effect and hydrogen-bonded supra­molecular motif in 5-(3-fluoro-4-methoxy­phenyl)-1-[(3-fluoro-4-methoxy­phenyl)amino­methyl]-1,3,5-triazinane-2-thione

In the title compound, C₁₈H₂₀F₂N₄O₂S, the triazinane-2-thione ring adopts an envelope conformation, the ring substituents lie on the same side of the mean plane of the heterocyclic ring and the exo lp—N—C—N_triaz unit (lp is a lone pair and triaz is the triazinane ring) exhibits an anti­periplanar orientation, which is shown to be governed by strong anomeric effects. Mol­ecules are linked into a complex three-dimensional framework by a combination of two N—H...S hydrogen bonds, three C—H...F hydrogen bonds and a π–π stacking inter­action.

S1. Comment

The anomeric effect is well recognized as one of the most important factors in the conformational analysis of systems containing geminal heteroatoms. It generally manifests itself as the propensity of an electronegative substituent at atom C1 of a pyranose ring to occupy an axial orientation (Scheme 1; Edward, 1955), despite unfavourable steric interaction with H atoms at C3 and C5. Similar conformational preferences have also been found in many heterocycles. This axial conformational preference is now termed the generalized anomeric effect. The effect is not restricted to heterocyclic systems, and evidence for its existence in acyclic compounds has also been found (Narasimhamurthy et al., 1990; Christen et al., 1996; Gobbato et al., 1997). Thus, the term `anomeric effect' has been generalized to refer to the conformational preference of an lp—X—Z—Y moiety for an antiperiplanar orientation of the lone pair (lp) to the Z—Y bond, where X represents an atom possessing lone pairs, Z is usually a C atom and Y denotes an atom more electronegative than Z.

Several theoretical models have been proposed to account for the origin of this effect. Although dipolar electrostatic interactions were first considered as its origin (Edward, 1955; Perrin et al., 1994; Pinto et al., 1988), they failed to explain the structural changes observed in the axial conformation, such as the decrease in the X—Z bond length, the increase in the Z—Y bond distance and the opening of the X—Z—Y angle. To explain these conformational preferences and changes in bond parameters, a stereoelectronic model (SM) has been proposed (Wiberg & Rablen, 1993). The SM considers that the stabilization of the antiperiplanar conformation results from the delocalization of one of the lps on X to the Z—Y σ* antibonding orbital, which takes place when the lp—X—Y—Z fragment adopts an antiperiplanar orientation. This stereoelectronic interaction is denoted as n(X) → σ*(Y—Z) and its validity has been well examined by X-ray analysis (Uehara et al., 1999; Ellenik & Magnusson, 1994; Juaristi & Cuevas, 1993; Kakanejadifard & Farnia, 1997; Zhang et al., 2009). If we concentrate on the N—C—N fragment, many experimental results have indicated that lp—N—C—N is in an antiperiplanar conformation, and the n(N)→σ*(C—N) interaction is the dominant factor in determining the conformational preference.

On the other hand, some N—C—N-containing compounds have been studied using both the quantum theory of atoms in molecules and X-ray analysis (Eskandari et al., 2007; Dong et al., 1999; Fun & Kia, 2008). The results show that the lp—N—C—N units in 1,3-diazacyclohexanes and 1,3,5-triazinane prefer the gauche orientation (Scheme 2). Thus, the conformational preferences of these N—C—N units are not in line with the SM of the anomeric effect. In contrast, these variations can be explained on the basis of the steric interactions.

However, despite these two different conformations and two interpretations for lp—N—C—N fragments, no studies of the anomeric effect, to our knowledge, have involved the 5-aryl-1-[(arylamino)methyl]-1,3,5-triazinane-2-thiones to date. Unlike the previously studied N—C—N units, the N(thioureido)—C—N(arylamine) fragments in 5-aryl-1-[(arylamino)methyl]-1,3,5-triazinane-2-thiones have two environmentally diverse N atoms. The concrete role they play in the conformational effect is our chief concern. Therefore, we report here the results of our studies of the anomeric effects and supramolecular structure of one such compound, the title compound, (I) (Fig. 1).

In (I), the triazinane-2-thione ring adopts an envelope conformation. Atom N1 is the flap atom, displaced by 0.636 (3) Å from the plane of the other five atoms. The N3 anilinomethyl and N1 phenyl groups lie on the same side of the heterocycle. The conformation is similar to those in our previously reported compounds (Zhang et al., 2008). However, the N4 lp adopts an antiperiplanar orientation with respect to the N3—C4 bond, which is unexpected and completely different from what has been observed in other N-containing heterocycles (Eskandari et al., 2007; Dong et al., 1999; Fun & Kia, 2008). This shows that the orientation of the N4 lp is not caused incidentally by the crystal packing or by intramolecular π–π or C—H···π interactions, but suggests the existence of anomeric effects in the exo N3—C4—N4 fragment. This can be further confirmed by some correlative geometric parameters (Table 1).

In (I), the endo residues, N1—C1—N2 and N1—C2—N3, are similar in chemical environment to the exo N3—C4—N4 fragment, and their bond lengths are consistent with the usual value for N—Csp³ bonds (1.44–1.47 Å; Glidewell et al., 2003; Nesterov et al., 2003; Akkurt et al., 2007; Ma et al. 1996). Therefore, the endo fragments N1—C1—N2 and N1—C2—N3 in (I) were selected as the model fragments. As shown in Table 1, the N4—C4 bond is much shorter than the corresponding N1—C1 and N1—C2 bonds, while the C4—N3 bond is much longer than the C1—N2 and C2—N3 bonds. The observed conformation, the remarkable lengthening of the N3—C4 bond and the significant shortening of the N4—C4 bond all point to the conclusion that there is a strong anomeric effect in the exo N3—C4—N4 unit. The existence of the anomeric effect was also further verified via the opening of the N4—C4—N3 angle relative to the angles N1—C1—N2 and N1—C2—N3 (Table 1). This interaction is best rationalized in terms of the `negative hyperconjugation' of the N4 p electron pair with the adjacent antibonding orbital of C4—N3, and it is the interaction that requires the N3—C4 bond to adopt an antiperiplanar orientation with respect to the N4 lp.

The molecules of (I) are linked into a complex three-dimensional framework by six weak intermolecular interactions, two N—H···S hydrogen bonds, three C—H···F hydrogen bonds (Table 2) and one π–π stacking interaction. However, the structure can be easily analyzed from an edge-fused dimer. Thioureido atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor to thiocarbonyl atom S1 in the molecule at (1 - x, 1 - y, -z), so generating by inversion a dimer centred at (1/2, 1/2, 0) and characterized by the usual R₂²(8) (Bernstein et al., 1995) graph-set motif (Fig. 2). Such dimers, as the backbone building units, are further linked into a two-dimensional network by N—H···S and C—H···F hydrogen bonds (Table 2). Imino atom N4 in the molecule at (x, y, z), part of the dimer centred at (1/2, 1/2, 0), acts as a hydrogen-bond donor to the atom S1 in the molecule at (x - 1, y, z), part of the dimer centred at (-1/2, 1/2, 0). Meanwhile, phenyl atom C10 and methyl atom C18 in the molecule at (1 - x, 1 - y, -z) act as hydrogen-bond donors to, respectively, atoms F1 and F2 in the molecule at (-x, 1 - y, -z), so generating by inversion and translation a multiple hydrogen-bonded chain parallel to [100] (Fig. 2). Chains of this type are laterally linked into a sheet by another C—H···F interaction (Table 2). Methyl atom C11 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H11B, to atom F2 in the molecule at (-x, -y, 1 - z), thus forming by inversion and translation a hydrogen-bonded sheet parallel to (011) (Fig. 2). Two such sheets, related to one another by a 2₁ screw axis along (x, 1/2, 1/2), pass through each unit cell, and adjacent sheets are linked through a π–π stacking interaction to build up a three-dimensional framework. The C12–C17 rings in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.556 (1) Å; the ring-centroid separation is 3.644 (1) Å, corresponding to a ring-centroid offset of 0.797 (1) Å (Fig. 3). Propagation of the motif by the space group links each (011) sheet to the two neighbouring sheets, so linking all of the sheets into a complex three-dimensional framework.

In conclusion, analysis of the X-ray crystallographic structural parameters in (I) has revealed that there is only a stereoelectronic interaction in the exo N(thioureido)—C—N(arylamine) fragment, where the arylamine atom N4 acts as an lp donor to the thioureido N3—C4 σ* antibonding orbital, and that the supramolecular structure exhibits a complex three-dimensional packing arrangement via a combination of two N—H···S hydrogen bonds, three C—H···F hydrogen bonds and a π–π stacking interaction.

S2. Experimental

Compound (I) was obtained from our laboratory (Reference to synthesis?) and crystals suitable for X-ray analysis were obtained by recrystallization from dimethylformamide.

S3. Refinement

All H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 (aromatic), 0.97 (CH₂) or 0.96 Å (CH₃) and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N) (1.5 for methyl C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a sheet parallel to (011). For the sake of clarity, H atoms not involved in the motif shown have been omitted. Intermolecular interactions are represented by dashed lines. Selected atoms are labelled. [Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, -y, 1 - z; (iii) 1 + x, y, z; (iv) x - 1, y, z].
	Fig. 3. Part of the crystal structure of compound (I), showing the π–π stacking interaction that links the (011) sheets. For the sake of clarity, all H atoms have been omitted. [Symmetry code: (v) 1 - x, 1 - y, 1 - z].

5-(3-fluoro-4-methoxyphenyl)-1-[(3-fluoro-4-methoxyphenyl)aminomethyl]- 1,3,5-triazinane-2-thione

Crystal data

C18H20F2N4O2S	Z = 2
Mr = 394.44	F(000) = 412
Triclinic, P1	Dx = 1.447 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6019 (8) Å	Cell parameters from 2659 reflections
b = 11.1195 (13) Å	θ = 3.0–25.5°
c = 13.9076 (17) Å	µ = 0.22 mm^−1
α = 106.693 (1)°	T = 296 K
β = 102.362 (1)°	Block, colourless
γ = 103.715 (1)°	0.31 × 0.28 × 0.23 mm
V = 905.31 (19) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3341 independent reflections
Radiation source: fine-focus sealed tube	2683 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 25.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.935, Tmax = 0.951	k = −13→13
6772 measured reflections	l = −16→16

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.2709P] where P = (Fo^2 + 2Fc^2)/3
3341 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.24 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
S1	0.23235 (9)	0.30856 (5)	−0.04874 (4)	0.05375 (16)
F1	−0.62384 (18)	−0.05474 (14)	0.24186 (11)	0.0721 (4)
F2	0.0469 (2)	0.32005 (16)	0.50105 (12)	0.0902 (5)
O1	−0.2537 (2)	−0.09836 (15)	0.30595 (13)	0.0663 (4)
O2	0.3728 (2)	0.22553 (15)	0.50330 (11)	0.0612 (4)
N1	0.1966 (3)	0.53756 (15)	0.26436 (12)	0.0518 (4)
N2	0.3653 (3)	0.51616 (16)	0.12691 (12)	0.0559 (4)
H2	0.4816	0.5355	0.1084	0.067*
N3	0.0144 (2)	0.38053 (15)	0.08834 (11)	0.0459 (4)
N4	−0.3316 (3)	0.22545 (17)	0.06919 (14)	0.0581 (4)
H4	−0.4429	0.2533	0.0664	0.070*
C1	0.3618 (4)	0.60429 (19)	0.22739 (16)	0.0618 (6)
H1A	0.5039	0.6328	0.2794	0.074*
H1B	0.3319	0.6823	0.2183	0.074*
C2	−0.0081 (3)	0.4776 (2)	0.18020 (15)	0.0545 (5)
H2A	−0.0526	0.5459	0.1595	0.065*
H2B	−0.1205	0.4336	0.2048	0.065*
C3	0.1997 (3)	0.40753 (18)	0.06202 (14)	0.0443 (4)
C4	−0.1813 (3)	0.2665 (2)	0.01638 (15)	0.0553 (5)
H4A	−0.2550	0.2913	−0.0395	0.066*
H4B	−0.1342	0.1927	−0.0158	0.066*
C5	−0.2572 (3)	−0.01931 (18)	0.24626 (15)	0.0463 (4)
C6	−0.4521 (3)	0.00398 (18)	0.21346 (15)	0.0467 (4)
C7	−0.4804 (3)	0.08152 (18)	0.15476 (14)	0.0474 (4)
H7	−0.6153	0.0940	0.1346	0.057*
C8	−0.3054 (3)	0.14196 (17)	0.12523 (14)	0.0437 (4)
C9	−0.1091 (3)	0.11870 (19)	0.15612 (16)	0.0500 (5)
H9	0.0092	0.1569	0.1365	0.060*
C10	−0.0860 (3)	0.03925 (18)	0.21584 (16)	0.0506 (5)
H10	0.0478	0.0253	0.2357	0.061*
C11	−0.0492 (4)	−0.1131 (2)	0.34785 (19)	0.0692 (6)
H11A	−0.0010	−0.1573	0.2912	0.104*
H11B	−0.0647	−0.1647	0.3922	0.104*
H11C	0.0566	−0.0274	0.3885	0.104*
C12	0.2519 (3)	0.45361 (17)	0.32008 (13)	0.0441 (4)
C13	0.1229 (3)	0.42315 (19)	0.38210 (15)	0.0517 (5)
H13	0.0047	0.4544	0.3846	0.062*
C14	0.1714 (3)	0.3471 (2)	0.43909 (16)	0.0529 (5)
C15	0.3456 (3)	0.29858 (18)	0.44038 (14)	0.0464 (4)
C16	0.4728 (3)	0.3289 (2)	0.37880 (15)	0.0507 (5)
H16	0.5919	0.2982	0.3774	0.061*
C17	0.4253 (3)	0.40515 (19)	0.31837 (14)	0.0506 (5)
H17	0.5117	0.4235	0.2764	0.061*
C18	0.5573 (4)	0.1807 (2)	0.51179 (18)	0.0651 (6)
H18A	0.5484	0.1226	0.4438	0.098*
H18B	0.5601	0.1338	0.5600	0.098*
H18C	0.6884	0.2553	0.5373	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0602 (3)	0.0619 (3)	0.0455 (3)	0.0250 (3)	0.0179 (2)	0.0224 (2)
F1	0.0469 (7)	0.0922 (9)	0.0986 (10)	0.0201 (6)	0.0362 (7)	0.0563 (8)
F2	0.0990 (10)	0.1321 (13)	0.1154 (12)	0.0667 (10)	0.0783 (9)	0.0959 (11)
O1	0.0532 (8)	0.0749 (10)	0.0912 (11)	0.0182 (7)	0.0259 (8)	0.0580 (9)
O2	0.0640 (9)	0.0706 (9)	0.0674 (9)	0.0253 (7)	0.0227 (7)	0.0459 (8)
N1	0.0727 (11)	0.0432 (9)	0.0426 (9)	0.0156 (8)	0.0195 (8)	0.0209 (7)
N2	0.0660 (11)	0.0525 (10)	0.0475 (9)	0.0062 (8)	0.0228 (8)	0.0215 (8)
N3	0.0527 (9)	0.0494 (9)	0.0416 (8)	0.0177 (7)	0.0145 (7)	0.0237 (7)
N4	0.0475 (9)	0.0719 (11)	0.0721 (12)	0.0258 (9)	0.0184 (8)	0.0448 (10)
C1	0.0871 (16)	0.0434 (11)	0.0511 (12)	0.0054 (11)	0.0234 (11)	0.0220 (9)
C2	0.0704 (13)	0.0585 (12)	0.0525 (12)	0.0330 (11)	0.0247 (10)	0.0308 (10)
C3	0.0554 (11)	0.0473 (10)	0.0399 (10)	0.0189 (9)	0.0130 (8)	0.0286 (9)
C4	0.0545 (12)	0.0629 (13)	0.0492 (11)	0.0137 (10)	0.0084 (9)	0.0304 (10)
C5	0.0446 (10)	0.0428 (10)	0.0530 (11)	0.0106 (8)	0.0149 (8)	0.0220 (9)
C6	0.0377 (9)	0.0489 (11)	0.0530 (11)	0.0082 (8)	0.0188 (8)	0.0183 (9)
C7	0.0372 (9)	0.0537 (11)	0.0514 (11)	0.0165 (8)	0.0120 (8)	0.0184 (9)
C8	0.0418 (10)	0.0432 (10)	0.0456 (10)	0.0131 (8)	0.0103 (8)	0.0176 (8)
C9	0.0405 (10)	0.0531 (11)	0.0665 (12)	0.0141 (9)	0.0212 (9)	0.0327 (10)
C10	0.0384 (10)	0.0518 (11)	0.0698 (13)	0.0164 (9)	0.0161 (9)	0.0323 (10)
C11	0.0592 (13)	0.0822 (16)	0.0825 (16)	0.0229 (12)	0.0168 (11)	0.0559 (14)
C12	0.0548 (11)	0.0390 (9)	0.0346 (9)	0.0085 (8)	0.0133 (8)	0.0128 (8)
C13	0.0577 (12)	0.0583 (12)	0.0538 (11)	0.0252 (10)	0.0264 (10)	0.0287 (10)
C14	0.0582 (12)	0.0631 (12)	0.0536 (11)	0.0205 (10)	0.0302 (10)	0.0337 (10)
C15	0.0514 (11)	0.0448 (10)	0.0419 (10)	0.0099 (9)	0.0126 (8)	0.0194 (8)
C16	0.0478 (11)	0.0590 (12)	0.0496 (11)	0.0185 (9)	0.0168 (9)	0.0229 (9)
C17	0.0540 (11)	0.0575 (12)	0.0446 (10)	0.0124 (9)	0.0223 (9)	0.0232 (9)
C18	0.0764 (15)	0.0612 (13)	0.0655 (14)	0.0306 (12)	0.0178 (12)	0.0294 (11)

Geometric parameters (Å, º)

C5—O1	1.372 (2)	C1—H1A	0.9700
C5—C10	1.376 (2)	C1—H1B	0.9700
C5—C6	1.380 (3)	C2—N1	1.445 (3)
C6—F1	1.363 (2)	C2—N3	1.478 (2)
C6—C7	1.364 (3)	C2—H2A	0.9700
C7—C8	1.396 (3)	C2—H2B	0.9700
C7—H7	0.9300	C12—C17	1.377 (3)
C8—C9	1.384 (2)	C12—C13	1.389 (2)
C8—N4	1.390 (2)	C12—N1	1.436 (2)
C9—C10	1.387 (2)	C13—C14	1.360 (3)
C9—H9	0.9300	C13—H13	0.9300
C10—H10	0.9300	C14—F2	1.358 (2)
C11—O1	1.419 (2)	C14—C15	1.380 (3)
C11—H11A	0.9600	C15—O2	1.367 (2)
C11—H11B	0.9600	C15—C16	1.376 (3)
C11—H11C	0.9600	C16—C17	1.395 (3)
C4—N4	1.422 (2)	C16—H16	0.9300
C4—N3	1.490 (2)	C17—H17	0.9300
C4—H4A	0.9700	C18—O2	1.416 (2)
C4—H4B	0.9700	C18—H18A	0.9600
C3—N2	1.339 (2)	C18—H18B	0.9600
C3—N3	1.342 (2)	C18—H18C	0.9600
C3—S1	1.7063 (19)	N4—H4	0.8600
C1—N1	1.442 (2)	N2—H2	0.8600
C1—N2	1.467 (2)
O1—C5—C10	126.63 (17)	N1—C2—H2B	109.5
O1—C5—C6	116.69 (16)	N3—C2—H2B	109.5
C10—C5—C6	116.67 (16)	H2A—C2—H2B	108.1
F1—C6—C7	119.09 (16)	C17—C12—C13	118.53 (17)
F1—C6—C5	117.33 (16)	C17—C12—N1	124.77 (16)
C7—C6—C5	123.59 (16)	C13—C12—N1	116.67 (17)
C6—C7—C8	119.47 (17)	C14—C13—C12	119.29 (18)
C6—C7—H7	120.3	C14—C13—H13	120.4
C8—C7—H7	120.3	C12—C13—H13	120.4
C9—C8—N4	122.55 (16)	F2—C14—C13	118.84 (17)
C9—C8—C7	117.96 (16)	F2—C14—C15	117.45 (16)
N4—C8—C7	119.47 (16)	C13—C14—C15	123.68 (17)
C8—C9—C10	121.03 (17)	O2—C15—C16	127.08 (18)
C8—C9—H9	119.5	O2—C15—C14	116.07 (16)
C10—C9—H9	119.5	C16—C15—C14	116.85 (17)
C5—C10—C9	121.27 (17)	C15—C16—C17	120.75 (18)
C5—C10—H10	119.4	C15—C16—H16	119.6
C9—C10—H10	119.4	C17—C16—H16	119.6
O1—C11—H11A	109.5	C12—C17—C16	120.89 (17)
O1—C11—H11B	109.5	C12—C17—H17	119.6
H11A—C11—H11B	109.5	C16—C17—H17	119.6
O1—C11—H11C	109.5	O2—C18—H18A	109.5
H11A—C11—H11C	109.5	O2—C18—H18B	109.5
H11B—C11—H11C	109.5	H18A—C18—H18B	109.5
N4—C4—N3	112.62 (16)	O2—C18—H18C	109.5
N4—C4—H4A	109.1	H18A—C18—H18C	109.5
N3—C4—H4A	109.1	H18B—C18—H18C	109.5
N4—C4—H4B	109.1	C8—N4—C4	122.49 (16)
N3—C4—H4B	109.1	C8—N4—H4	118.8
H4A—C4—H4B	107.8	C4—N4—H4	118.8
N2—C3—N3	117.87 (17)	C3—N3—C2	119.30 (16)
N2—C3—S1	119.38 (15)	C3—N3—C4	120.73 (16)
N3—C3—S1	122.75 (15)	C2—N3—C4	119.12 (16)
N1—C1—N2	110.71 (16)	C12—N1—C1	117.62 (17)
N1—C1—H1A	109.5	C12—N1—C2	114.78 (15)
N2—C1—H1A	109.5	C1—N1—C2	109.06 (15)
N1—C1—H1B	109.5	C3—N2—C1	124.40 (17)
N2—C1—H1B	109.5	C3—N2—H2	117.8
H1A—C1—H1B	108.1	C1—N2—H2	117.8
N1—C2—N3	110.60 (16)	C5—O1—C11	117.01 (15)
N1—C2—H2A	109.5	C15—O2—C18	117.81 (16)
N3—C2—H2A	109.5
O1—C5—C6—F1	−0.9 (3)	C9—C8—N4—C4	16.4 (3)
C10—C5—C6—F1	179.19 (17)	C7—C8—N4—C4	−165.55 (18)
O1—C5—C6—C7	179.25 (17)	N3—C4—N4—C8	−82.2 (2)
C10—C5—C6—C7	−0.7 (3)	N2—C3—N3—C2	6.5 (2)
F1—C6—C7—C8	−179.94 (16)	S1—C3—N3—C2	−174.36 (12)
C5—C6—C7—C8	−0.1 (3)	N2—C3—N3—C4	175.87 (15)
C6—C7—C8—C9	0.9 (3)	S1—C3—N3—C4	−5.0 (2)
C6—C7—C8—N4	−177.31 (17)	N1—C2—N3—C3	−38.6 (2)
N4—C8—C9—C10	177.22 (18)	N1—C2—N3—C4	151.90 (15)
C7—C8—C9—C10	−0.9 (3)	N4—C4—N3—C3	159.98 (16)
O1—C5—C10—C9	−179.27 (19)	N4—C4—N3—C2	−30.6 (2)
C6—C5—C10—C9	0.7 (3)	C17—C12—N1—C1	−17.3 (3)
C8—C9—C10—C5	0.1 (3)	C13—C12—N1—C1	160.84 (17)
C17—C12—C13—C14	0.1 (3)	C17—C12—N1—C2	113.1 (2)
N1—C12—C13—C14	−178.13 (18)	C13—C12—N1—C2	−68.8 (2)
C12—C13—C14—F2	178.74 (18)	N2—C1—N1—C12	82.6 (2)
C12—C13—C14—C15	0.8 (3)	N2—C1—N1—C2	−50.3 (2)
F2—C14—C15—O2	1.1 (3)	N3—C2—N1—C12	−74.42 (19)
C13—C14—C15—O2	178.99 (19)	N3—C2—N1—C1	59.98 (19)
F2—C14—C15—C16	−178.79 (18)	N3—C3—N2—C1	3.0 (3)
C13—C14—C15—C16	−0.9 (3)	S1—C3—N2—C1	−176.13 (15)
O2—C15—C16—C17	−179.90 (18)	N1—C1—N2—C3	19.9 (3)
C14—C15—C16—C17	−0.1 (3)	C10—C5—O1—C11	5.4 (3)
C13—C12—C17—C16	−1.0 (3)	C6—C5—O1—C11	−174.51 (19)
N1—C12—C17—C16	177.09 (17)	C16—C15—O2—C18	3.6 (3)
C15—C16—C17—C12	1.0 (3)	C14—C15—O2—C18	−176.26 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	0.86	2.68	3.469 (2)	152
N4—H4···S1^ii	0.86	2.69	3.456 (2)	148
C10—H10···F1^iii	0.93	2.53	3.434 (3)	165
C11—H11B···F2^iv	0.96	2.59	3.535 (3)	169
C18—H18C···F2^iii	0.96	2.51	3.292 (3)	139

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