The search for formal electrostatic effects on mol­ecular conformation and crystal packing: crystal structure of 2,2′′-disubstituted (H versus PPh₂) 1,1′-(1,2-phenyl­ene)bis­(3-methyl-1H-imidazol-3-ium) bis­(tri­fluoro­methane­sulfonate)

Electrostatic inter­actions between localized integral charges make the stability and structure of highly charged small and rigid organics intriguing. Can σ/π-electron delocalization compensate reduced conformational freedom by lowering the repulsion between identical charges? The crystal structure of the title salt, C₁₄H₁₆N₄²⁺·2CF₃SO₃⁻, (2), is described and compared with that of the 2,2′′-bis­(di­phenyl­phosphan­yl) derivative, (4). The conformations of the dications and their inter­actions with neighbouring tri­fluoro­methane­sulfonate anions are first analyzed from the standpoint of formal electrostatic effects. Neither cation exhibits any geometrical strain induced by the intrinsic repulsion between the positive charges. In contrast, the relative orientation of the imidazolium rings [i.e. anti for (2) and syn for (4)] is controlled by different configurations of the inter­actions with the closest tri­fluoro­methane­sulfonate anions. The long-range arrangement is also found to be specific: beyond the formal electrostatic packing, C—H...O and C—H...F contacts have no definite `hydrogen-bond' character but allow the delineation of layers, which are either pleated or flat in the packing of (2) or (4), respectively.

S1. Introduction

\ Consideration of electrostatic inter­actions between localized integral charges, being either repulsive or attractive in nature, makes the stability and structure of highly charged small and rigid organics intriguing; the issue is how σ/π-electron delocalization can compensate reduced conformational freedom by lowering the repulsion between identical charges. In this spirit, heteroaromatic systems provide both π-conjugation and rigidity features. The issue is hereafter addressed within the context of two neighbouring imidazolium rings at a rigid o-phenyl­ene core; N,N'-di­methyl­ation of 1,2-bis­(1H-imidazol-1-yl)benzene, (1) (So, 1992), affords the corresponding bis-imidazolium salt 1,1'-(1,2-phenyl­ene)bis­(3-methyl-1H-imidazol-3-ium) bis­(tri­fluoro­methane­sulfonate), (2) (see Scheme 1). The latter was used as the conjugated acid of a neutral bis-N-heterocyclic carbene (NHC) acting as a cis-chelating ligand in Pd^II (Tubaro et al., 2006) and Rh^I complexes such as (3) (Canac et al., 2008). The two positive charges of (2) can, however, be preserved in the coordination sphere of metal centres upon prior C2-phosphinylation of the imidazolium rings: the resulting bis-imidazoliophosphine, 1,1'-(1,2-phenyl­ene)bis-2-(di­phenyl­phosphanyl)-3-methyl-1H-imidazol-3-\ ium] bis­(tri­fluoro­methane­sulfonate), (4) (Canac et al., 2009), was shown to act as a trans-coordinating ligand in both Pd^II (Canac et al., 2011) and Rh^I complexes, such as the carbonyl­chloridorhodium(I) complex (5) (Canac et al., 2009) (Scheme 1).

The results of a single-crystal X-ray diffraction experiment on (2) are presented. The structure is compared to that of the related bis-imidazoliophosphine (4) reported recently (Canac et al., 2011).

S2. Experimental

S2.1. Synthesis and crystallization

The preparation and analytical data (¹H and ¹³C NMR spectroscopy, HRMS and melting point) of (2) and (4) have been reported previously [see Canac et al. (2008) and Canac et al. (2009), respectively]. Colourless crystals were obtained by recrystallization from CH₂Cl₂/Et₂O at 273 K for (2) and from CH₃CN/Et₂O at 253 K for (4).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010). The molecular view and local ionic association of (2) are shown in Fig. 1.

S3. Results and discussion

The title salt (2) crystallizes in the centrosymmetric space group P2₁/c with one bis­imidazolium dication and two tri­fluoro­methane­sulfonate anions in the asymmetric unit (Fig. 1). Data collection at low temperature (100 K) allowed minimization of the displacement parameters, especially for the tri­fluoro­methane­sulfonate anions. Both the molecular conformation and the crystal packing are sequentially discussed below.

S3.1. Molecular conformation

In the dication of salt (2), the planes of the two imidazolium rings, denoted A (atoms N2/C1/N1/C2/C3) and B (atoms N3/C12/N4/C11/C10) are nearly planar, the maximum deviations from the mean planes being 0.0038 (8) Å for ring A (atom C2) and 0.0021 (8) Å for ring B (atom C11). Phenyl­ene ring C is also nearly planar, with a maximum deviation from the mean plane of 0.0188 (8) Å (atom C9). The anti­cipated aromatic character of phenyl­ene ring C is further confirmed by a mean C—C bond length of 1.394 Å {corresponding to the value of the harmonic oscillator model for equivalent Kékulé structures: ([1.54 + 2(1.33)]/3 = 1.40 Å} (Kruszewski & Krygowski, 1972). The geometric aromatic character of imidazolium rings A and B is less pronounced, with quasi-equalized bond lengths in the N—C—N units (Table 2), but much greater lengths for the four other C—N bonds (1.390±0.003 Å; Table 2). It is also noticeable that the C═ C bond lengths (C2═C3 and C10═C11; Table 2) in the A and B rings are slightly elongated with respect to related C—C bonds in imidazolium salts of the general type N-aryl-N'-R-1H-imidazolium; mean value = 1.343 Å for 121 structures found in the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014).

Regarding strain and conformational features, the formal +/+ electrostatic repulsion between imidazolium rings A and B has no significant effect on the standard valence shell electron pair repulsion (VSEPR) bond angles at the aromatic C atoms C4 and C9 (Table 2). The dihedral angles between the mean plane of ring C and those of imidazolium rings A and B are 48.52 (4) and 57.50 (3)°, respectively, and the angle between the mean planes of rings A and B is 56.90 (4)°, with an anti orientation of the two imidazolium rings (the N-methyl groups at C13 and C14 are located on opposite sides of the mean plane of ring C). The contacts of the dication with two different pairs of tri­fluoro­methane­sulfonate anions occur at the amidinium centres C1—H11 and C12—H121; the inter­actions of the O atoms correspond to tight van der Waals contacts with both C atoms [C1···O3 = 3.009 (1) Å, C1···O4 = 2.907 (2) Å, C12···O2^v = 2.918 (2) Å and C12···O5ⁱⁱ = 3.363 (2) Å; symmetry codes: (ii) x, −y + 1/2, z − 1/2; (v) −x + 2, −y + 1, −z + 1] and H atoms [H11···O3 = 2.61 Å and C1—H11···O3 = 108°; H11···O4 = 2.66 Å and C1—H11···O4 = 96°; H121···O2^v = 2.45 Å and C12—H121···O2^v = 112°; H121···O5ⁱⁱ = 2.52 Å and C12—H121···O5ⁱⁱ = 153°]. In spite of the negative charge of the O atoms and the acidic character of the amidinium H atoms, no true C—H···O hydrogen bond is thus evidenced.

The structure of (2) deserves comparison with the previously reported X-ray crystal structure of the bis-di­phenyl­phosphin derivative (4) (Fig. 2; Canac et al., 2011). In contrast to (2), the imidazolium rings of (4) are in a syn orientation with respect to the central phenyl­ene ring [here also without a significant strain effect of the +/+ formal electrostatic repulsion: N3—C9—C4 = 121.6 (4)° and N2—C4—C9 = 120.2 (4)°]. Although a syn–anti equilibrium was evidenced in solution (Canac et al., 2009), the syn conformation found in the solid state was inter­preted to be driven by a PN₂C⁺···O⁻···⁺CN₂P electrostatic pincer inter­action at one of the O atoms of the two tri­fluoro­methane­sulfonate anions [O5···C1 = 3.382 (6) Å and O5···C10 = 3.261 (6) Å; see Scheme 2 and Fig. 2]. No significant inter­action occurs with the second tri­fluoro­methane­sulfonate (TfO) anion [minimum nonbonding TfO···C distance O2A···C10ⁱⁱⁱ = 3.831 (7) Å; symmetry code: (iii) −x + 1/2, y − 1/2, −z + 1/2].

S3.2. Crystal Packing

In the crystal structure of (2), an anti orientation of imidazolium rings A and B with respect to phenyl­ene ring C (see above) induces a pleated (zigzag) layer pattern (Fig. 3). In addition to the formal electrostatic attraction between the imidazolium and the tri­fluoro­methane­sulfonate anions, weak C—H···O inter­actions [with a minimum C···O distance of 3.1280 (11) Å; Table 2] and weak C—H···F inter­actions [with a minimum C···F distance of 3.144 (2) Å; Table 3] contribute to the global stabilization of the three-dimensional network.

In the case of (4), weak C—H···O inter­actions between the bis-imidazolium and tri­fluoro­methane­sulfonate ions [with a minimum C···O distance of 3.086 (7) Å; Fig. 4 and Table 4] allow the identification of planar layers along the a and b axes. The crystal packing is further stabilized by weak C—H···F inter­actions [with a minimum C···F distance of 3.301 (9) Å; Fig. 2 and Table 4]. In spite of the occurrence of five phenyl­ene or phenyl rings and face-to-face positioning between them in the crystal structure of (4), an analysis by PLATON (Spek, 2009) does not give any evidence of significant π–π inter­actions.

S4. Conclusion

The behaviour of 1,2-bis­(1H-imidazol-1-yl)benzene, (1), and its analogues as ligands of transition metal centres has been extensively explored, especially for catalytic purposes (Albrecht et al., 2002; Rentzsch et al., 2009; Subramanium et al., 2011; Munz et al., 2013; Howell et al., 2014). However, despite the report of its symmetric salt [one step on from (1)], the structure of the 3,3'-di­methyl­ated 1,1'-(1,2-phenyl­ene)bis­(3-methyl-1H-imidazol-3-ium)dication seen in (2) has not been reported in the CSD. It is finally noteworthy that in spite of a looser local ionic association in (2), the crystal density of (2) (D_x = 1.69 Mg m⁻³) is significantly greater than the crystal density of the 2,2'-bis (di­phenyl­phosphanyl) analogue, (4) (D_x = 1.17 Mg m⁻³). The tight electrostatic pincer association occurring in the solid-state structure of (4) is indeed compensated and globally diluted by large voids contributing for a total of ca 25–30% of the crystal volume.

Structure description

\ Consideration of electrostatic inter­actions between localized integral charges, being either repulsive or attractive in nature, makes the stability and structure of highly charged small and rigid organics intriguing; the issue is how σ/π-electron delocalization can compensate reduced conformational freedom by lowering the repulsion between identical charges. In this spirit, heteroaromatic systems provide both π-conjugation and rigidity features. The issue is hereafter addressed within the context of two neighbouring imidazolium rings at a rigid o-phenyl­ene core; N,N'-di­methyl­ation of 1,2-bis­(1H-imidazol-1-yl)benzene, (1) (So, 1992), affords the corresponding bis-imidazolium salt 1,1'-(1,2-phenyl­ene)bis­(3-methyl-1H-imidazol-3-ium) bis­(tri­fluoro­methane­sulfonate), (2) (see Scheme 1). The latter was used as the conjugated acid of a neutral bis-N-heterocyclic carbene (NHC) acting as a cis-chelating ligand in Pd^II (Tubaro et al., 2006) and Rh^I complexes such as (3) (Canac et al., 2008). The two positive charges of (2) can, however, be preserved in the coordination sphere of metal centres upon prior C2-phosphinylation of the imidazolium rings: the resulting bis-imidazoliophosphine, 1,1'-(1,2-phenyl­ene)bis-2-(di­phenyl­phosphanyl)-3-methyl-1H-imidazol-3-\ ium] bis­(tri­fluoro­methane­sulfonate), (4) (Canac et al., 2009), was shown to act as a trans-coordinating ligand in both Pd^II (Canac et al., 2011) and Rh^I complexes, such as the carbonyl­chloridorhodium(I) complex (5) (Canac et al., 2009) (Scheme 1).

The results of a single-crystal X-ray diffraction experiment on (2) are presented. The structure is compared to that of the related bis-imidazoliophosphine (4) reported recently (Canac et al., 2011).

The title salt (2) crystallizes in the centrosymmetric space group P2₁/c with one bis­imidazolium dication and two tri­fluoro­methane­sulfonate anions in the asymmetric unit (Fig. 1). Data collection at low temperature (100 K) allowed minimization of the displacement parameters, especially for the tri­fluoro­methane­sulfonate anions. Both the molecular conformation and the crystal packing are sequentially discussed below.

In the dication of salt (2), the planes of the two imidazolium rings, denoted A (atoms N2/C1/N1/C2/C3) and B (atoms N3/C12/N4/C11/C10) are nearly planar, the maximum deviations from the mean planes being 0.0038 (8) Å for ring A (atom C2) and 0.0021 (8) Å for ring B (atom C11). Phenyl­ene ring C is also nearly planar, with a maximum deviation from the mean plane of 0.0188 (8) Å (atom C9). The anti­cipated aromatic character of phenyl­ene ring C is further confirmed by a mean C—C bond length of 1.394 Å {corresponding to the value of the harmonic oscillator model for equivalent Kékulé structures: ([1.54 + 2(1.33)]/3 = 1.40 Å} (Kruszewski & Krygowski, 1972). The geometric aromatic character of imidazolium rings A and B is less pronounced, with quasi-equalized bond lengths in the N—C—N units (Table 2), but much greater lengths for the four other C—N bonds (1.390±0.003 Å; Table 2). It is also noticeable that the C═ C bond lengths (C2═C3 and C10═C11; Table 2) in the A and B rings are slightly elongated with respect to related C—C bonds in imidazolium salts of the general type N-aryl-N'-R-1H-imidazolium; mean value = 1.343 Å for 121 structures found in the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014).

Regarding strain and conformational features, the formal +/+ electrostatic repulsion between imidazolium rings A and B has no significant effect on the standard valence shell electron pair repulsion (VSEPR) bond angles at the aromatic C atoms C4 and C9 (Table 2). The dihedral angles between the mean plane of ring C and those of imidazolium rings A and B are 48.52 (4) and 57.50 (3)°, respectively, and the angle between the mean planes of rings A and B is 56.90 (4)°, with an anti orientation of the two imidazolium rings (the N-methyl groups at C13 and C14 are located on opposite sides of the mean plane of ring C). The contacts of the dication with two different pairs of tri­fluoro­methane­sulfonate anions occur at the amidinium centres C1—H11 and C12—H121; the inter­actions of the O atoms correspond to tight van der Waals contacts with both C atoms [C1···O3 = 3.009 (1) Å, C1···O4 = 2.907 (2) Å, C12···O2^v = 2.918 (2) Å and C12···O5ⁱⁱ = 3.363 (2) Å; symmetry codes: (ii) x, −y + 1/2, z − 1/2; (v) −x + 2, −y + 1, −z + 1] and H atoms [H11···O3 = 2.61 Å and C1—H11···O3 = 108°; H11···O4 = 2.66 Å and C1—H11···O4 = 96°; H121···O2^v = 2.45 Å and C12—H121···O2^v = 112°; H121···O5ⁱⁱ = 2.52 Å and C12—H121···O5ⁱⁱ = 153°]. In spite of the negative charge of the O atoms and the acidic character of the amidinium H atoms, no true C—H···O hydrogen bond is thus evidenced.

The structure of (2) deserves comparison with the previously reported X-ray crystal structure of the bis-di­phenyl­phosphin derivative (4) (Fig. 2; Canac et al., 2011). In contrast to (2), the imidazolium rings of (4) are in a syn orientation with respect to the central phenyl­ene ring [here also without a significant strain effect of the +/+ formal electrostatic repulsion: N3—C9—C4 = 121.6 (4)° and N2—C4—C9 = 120.2 (4)°]. Although a syn–anti equilibrium was evidenced in solution (Canac et al., 2009), the syn conformation found in the solid state was inter­preted to be driven by a PN₂C⁺···O⁻···⁺CN₂P electrostatic pincer inter­action at one of the O atoms of the two tri­fluoro­methane­sulfonate anions [O5···C1 = 3.382 (6) Å and O5···C10 = 3.261 (6) Å; see Scheme 2 and Fig. 2]. No significant inter­action occurs with the second tri­fluoro­methane­sulfonate (TfO) anion [minimum nonbonding TfO···C distance O2A···C10ⁱⁱⁱ = 3.831 (7) Å; symmetry code: (iii) −x + 1/2, y − 1/2, −z + 1/2].

In the crystal structure of (2), an anti orientation of imidazolium rings A and B with respect to phenyl­ene ring C (see above) induces a pleated (zigzag) layer pattern (Fig. 3). In addition to the formal electrostatic attraction between the imidazolium and the tri­fluoro­methane­sulfonate anions, weak C—H···O inter­actions [with a minimum C···O distance of 3.1280 (11) Å; Table 2] and weak C—H···F inter­actions [with a minimum C···F distance of 3.144 (2) Å; Table 3] contribute to the global stabilization of the three-dimensional network.

In the case of (4), weak C—H···O inter­actions between the bis-imidazolium and tri­fluoro­methane­sulfonate ions [with a minimum C···O distance of 3.086 (7) Å; Fig. 4 and Table 4] allow the identification of planar layers along the a and b axes. The crystal packing is further stabilized by weak C—H···F inter­actions [with a minimum C···F distance of 3.301 (9) Å; Fig. 2 and Table 4]. In spite of the occurrence of five phenyl­ene or phenyl rings and face-to-face positioning between them in the crystal structure of (4), an analysis by PLATON (Spek, 2009) does not give any evidence of significant π–π inter­actions.

The behaviour of 1,2-bis­(1H-imidazol-1-yl)benzene, (1), and its analogues as ligands of transition metal centres has been extensively explored, especially for catalytic purposes (Albrecht et al., 2002; Rentzsch et al., 2009; Subramanium et al., 2011; Munz et al., 2013; Howell et al., 2014). However, despite the report of its symmetric salt [one step on from (1)], the structure of the 3,3'-di­methyl­ated 1,1'-(1,2-phenyl­ene)bis­(3-methyl-1H-imidazol-3-ium)dication seen in (2) has not been reported in the CSD. It is finally noteworthy that in spite of a looser local ionic association in (2), the crystal density of (2) (D_x = 1.69 Mg m⁻³) is significantly greater than the crystal density of the 2,2'-bis (di­phenyl­phosphanyl) analogue, (4) (D_x = 1.17 Mg m⁻³). The tight electrostatic pincer association occurring in the solid-state structure of (4) is indeed compensated and globally diluted by large voids contributing for a total of ca 25–30% of the crystal volume.

Synthesis and crystallization

The preparation and analytical data (¹H and ¹³C NMR spectroscopy, HRMS and melting point) of (2) and (4) have been reported previously [see Canac et al. (2008) and Canac et al. (2009), respectively]. Colourless crystals were obtained by recrystallization from CH₂Cl₂/Et₂O at 273 K for (2) and from CH₃CN/Et₂O at 253 K for (4).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010). The molecular view and local ionic association of (2) are shown in Fig. 1.

Computing details

Data collection: GEMINI (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2002); data reduction: CrysAlis PRO (Oxford Diffraction, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. View of the ionic structure of (2), showing the atom-numbering (Mercury; Macrae et al., 2006). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the ionic structure of (4) (CSD deposition number 829642; reference?), showing the atom-numbering (ball-and-stick model).
	Fig. 3. Packing diagram of (2), exhibiting C—H···O and C—H···F-stacked pleated layers (zigzag along the b axis), the internal cohesion of which can be mainly attributed to formal electrostatics.
	Fig. 4. Packing diagram of (4), showing layers along the a and b axes (green and yellow), with the main interactions responsible for the intrinsic and stacking cohesion indicated.

1,1'-(1,2-Phenylene)bis(3-methyl-1H-imidazol-3-ium) bis(trifluoromethanesulfonate)

Crystal data

C14H16N4^2+·2CF3O3S^−	F(000) = 1096
Mr = 538.45	Dx = 1.692 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25125 reflections
a = 11.37505 (13) Å	θ = 3–31°
b = 16.09785 (17) Å	µ = 0.35 mm^−1
c = 11.60677 (14) Å	T = 100 K
β = 96.0475 (11)°	Stick, colorless
V = 2113.53 (4) Å^3	0.30 × 0.15 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Gemini diffractometer	5692 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.024
φ & ω scans	θmax = 30.8°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2002)	h = −16→16
Tmin = 0.83, Tmax = 0.95	k = −22→22
63741 measured reflections	l = −16→16
6255 independent reflections

Refinement

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.037	Method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 7.87 5.71 6.74 1.57
S = 1.03	(Δ/σ)max = 0.002
5521 reflections	Δρmax = 0.43 e Å^−3
307 parameters	Δρmin = −0.38 e Å^−3
0 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.

Cosier, J. & Glazer, A·M., 1986. J. Appl. Cryst. 105–107.

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

	x	y	z	Uiso*/Ueq
C1	0.71376 (7)	0.35843 (5)	0.83935 (7)	0.0132
C2	0.55425 (7)	0.43368 (5)	0.78613 (7)	0.0146
C3	0.61222 (7)	0.42296 (5)	0.69102 (7)	0.0137
C4	0.79606 (7)	0.34484 (5)	0.65289 (7)	0.0115
C5	0.82570 (7)	0.26087 (5)	0.65653 (7)	0.0150
C6	0.90347 (8)	0.23055 (5)	0.58135 (8)	0.0184
C7	0.94882 (8)	0.28305 (6)	0.50108 (8)	0.0195
C8	0.92075 (8)	0.36740 (6)	0.49951 (8)	0.0164
C9	0.84620 (7)	0.39814 (5)	0.57686 (7)	0.0118
C10	0.84737 (7)	0.53768 (5)	0.67478 (7)	0.0129
C11	0.81580 (7)	0.61555 (5)	0.63821 (7)	0.0140
C12	0.77834 (7)	0.53111 (5)	0.48792 (7)	0.0140
C13	0.58510 (9)	0.38273 (6)	0.99477 (8)	0.0208
C14	0.72682 (9)	0.67888 (6)	0.44805 (8)	0.0211
C15	1.18412 (8)	0.43699 (7)	0.94517 (9)	0.0234
C16	0.46626 (8)	0.19381 (5)	0.75764 (7)	0.0157
N1	0.61880 (7)	0.39242 (5)	0.87714 (6)	0.0144
N2	0.71225 (6)	0.37591 (4)	0.72599 (6)	0.0109
N3	0.82313 (6)	0.48571 (4)	0.57938 (6)	0.0114
N4	0.77371 (6)	0.60978 (5)	0.52187 (6)	0.0143
O1	1.13344 (7)	0.30817 (4)	0.81942 (7)	0.0239
O2	1.11338 (7)	0.44402 (5)	0.72643 (7)	0.0255
O3	0.97278 (6)	0.40083 (4)	0.85946 (6)	0.0178
O4	0.63883 (7)	0.19745 (5)	0.91846 (7)	0.0254
O5	0.63356 (7)	0.08472 (5)	0.77742 (7)	0.0263
O6	0.49371 (7)	0.08631 (5)	0.92308 (6)	0.0226
S1	1.090136 (17)	0.392408 (12)	0.823237 (17)	0.0124
S2	0.570075 (18)	0.133562 (13)	0.855416 (17)	0.0143
F1	1.16670 (8)	0.39882 (6)	1.04432 (6)	0.0425
F2	1.29916 (6)	0.42872 (5)	0.93033 (8)	0.0391
F3	1.16272 (7)	0.51768 (5)	0.95785 (8)	0.0407
F4	0.39334 (5)	0.14513 (4)	0.68946 (5)	0.0248
F5	0.39988 (6)	0.24389 (4)	0.81657 (6)	0.0258
F6	0.52463 (5)	0.24220 (4)	0.68822 (5)	0.0209
H11	0.7709	0.3296	0.8827	0.0163*
H21	0.4839	0.4618	0.7940	0.0207*
H31	0.5916	0.4404	0.6173	0.0165*
H51	0.7928	0.2267	0.7071	0.0184*
H61	0.9264	0.1745	0.5825	0.0217*
H71	0.9983	0.2623	0.4487	0.0249*
H81	0.9510	0.4043	0.4462	0.0210*
H101	0.8792	0.5185	0.7463	0.0170*
H111	0.8218	0.6644	0.6783	0.0177*
H121	0.7549	0.5107	0.4155	0.0171*
H132	0.5670	0.4362	1.0262	0.0350*
H131	0.6469	0.3570	1.0431	0.0345*
H133	0.5138	0.3486	0.9907	0.0342*
H142	0.7531	0.6725	0.3738	0.0331*
H143	0.7583	0.7297	0.4814	0.0345*
H141	0.6434	0.6791	0.4448	0.0334*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0138 (3)	0.0135 (3)	0.0124 (3)	−0.0022 (3)	0.0012 (3)	0.0022 (3)
C2	0.0143 (3)	0.0138 (3)	0.0159 (4)	0.0021 (3)	0.0033 (3)	0.0009 (3)
C3	0.0135 (3)	0.0134 (3)	0.0144 (3)	0.0028 (3)	0.0019 (3)	0.0031 (3)
C4	0.0108 (3)	0.0115 (3)	0.0123 (3)	−0.0002 (2)	0.0013 (2)	−0.0013 (2)
C5	0.0152 (3)	0.0108 (3)	0.0184 (4)	0.0001 (3)	−0.0009 (3)	−0.0007 (3)
C6	0.0154 (4)	0.0129 (4)	0.0261 (4)	0.0021 (3)	−0.0007 (3)	−0.0063 (3)
C7	0.0153 (4)	0.0187 (4)	0.0249 (4)	−0.0002 (3)	0.0049 (3)	−0.0098 (3)
C8	0.0146 (3)	0.0172 (4)	0.0182 (4)	−0.0025 (3)	0.0060 (3)	−0.0051 (3)
C9	0.0118 (3)	0.0105 (3)	0.0133 (3)	−0.0008 (2)	0.0018 (3)	−0.0027 (2)
C10	0.0142 (3)	0.0121 (3)	0.0125 (3)	−0.0004 (3)	0.0025 (3)	−0.0016 (3)
C11	0.0142 (3)	0.0132 (3)	0.0150 (3)	0.0002 (3)	0.0032 (3)	−0.0005 (3)
C12	0.0148 (3)	0.0151 (4)	0.0123 (3)	−0.0020 (3)	0.0030 (3)	0.0017 (3)
C13	0.0235 (4)	0.0258 (4)	0.0142 (4)	−0.0009 (3)	0.0073 (3)	0.0007 (3)
C14	0.0233 (4)	0.0184 (4)	0.0218 (4)	0.0046 (3)	0.0028 (3)	0.0087 (3)
C15	0.0155 (4)	0.0271 (5)	0.0267 (5)	0.0004 (3)	−0.0020 (3)	−0.0079 (4)
C16	0.0141 (3)	0.0167 (4)	0.0159 (3)	−0.0013 (3)	0.0000 (3)	0.0030 (3)
N1	0.0150 (3)	0.0161 (3)	0.0124 (3)	−0.0013 (2)	0.0032 (2)	0.0011 (2)
N2	0.0112 (3)	0.0102 (3)	0.0114 (3)	0.0001 (2)	0.0018 (2)	0.0011 (2)
N3	0.0131 (3)	0.0104 (3)	0.0112 (3)	−0.0012 (2)	0.0029 (2)	−0.0004 (2)
N4	0.0142 (3)	0.0142 (3)	0.0148 (3)	0.0007 (2)	0.0032 (2)	0.0033 (2)
O1	0.0270 (3)	0.0134 (3)	0.0324 (4)	0.0020 (2)	0.0086 (3)	−0.0019 (3)
O2	0.0292 (4)	0.0275 (4)	0.0213 (3)	−0.0013 (3)	0.0101 (3)	0.0095 (3)
O3	0.0115 (3)	0.0229 (3)	0.0191 (3)	−0.0008 (2)	0.0026 (2)	0.0022 (2)
O4	0.0251 (3)	0.0211 (3)	0.0270 (3)	−0.0059 (3)	−0.0109 (3)	0.0011 (3)
O5	0.0284 (4)	0.0251 (4)	0.0259 (3)	0.0096 (3)	0.0059 (3)	0.0010 (3)
O6	0.0302 (4)	0.0201 (3)	0.0174 (3)	−0.0059 (3)	0.0020 (3)	0.0054 (2)
S1	0.01286 (9)	0.01196 (9)	0.01260 (9)	−0.00093 (6)	0.00293 (7)	0.00085 (6)
S2	0.01589 (10)	0.01231 (9)	0.01404 (9)	−0.00015 (6)	−0.00162 (7)	0.00201 (6)
F1	0.0398 (4)	0.0681 (6)	0.0173 (3)	0.0038 (4)	−0.0074 (3)	0.0004 (3)
F2	0.0126 (3)	0.0463 (4)	0.0569 (5)	−0.0003 (3)	−0.0035 (3)	−0.0123 (4)
F3	0.0329 (4)	0.0295 (4)	0.0587 (5)	−0.0020 (3)	−0.0004 (3)	−0.0264 (3)
F4	0.0207 (3)	0.0309 (3)	0.0210 (3)	−0.0088 (2)	−0.0065 (2)	0.0014 (2)
F5	0.0222 (3)	0.0270 (3)	0.0289 (3)	0.0091 (2)	0.0057 (2)	0.0017 (2)
F6	0.0225 (3)	0.0198 (3)	0.0202 (2)	−0.0025 (2)	0.0020 (2)	0.0083 (2)

Geometric parameters (Å, º)

N1—C1	1.3261 (11)	C8—C9	1.3894 (11)
N1—C2	1.3903 (11)	C8—H81	0.949
N1—C13	1.4647 (11)	C10—H101	0.923
N2—C1	1.3438 (10)	C11—H111	0.913
N2—C3	1.3913 (10)	C12—H121	0.915
N2—C4	1.4317 (10)	C13—H132	0.967
N3—C9	1.4347 (10)	C13—H131	0.948
N3—C10	1.3921 (10)	C13—H133	0.977
N3—C12	1.3441 (10)	C14—H142	0.947
N4—C11	1.3874 (11)	C14—H143	0.958
N4—C12	1.3290 (11)	C14—H141	0.945
N4—C14	1.4696 (11)	C15—S1	1.8282 (10)
C2—C3	1.3552 (11)	C15—F1	1.3376 (14)
C10—C11	1.3597 (11)	C15—F2	1.3443 (11)
C1—H11	0.907	C15—F3	1.3325 (13)
C2—H21	0.932	C16—S2	1.8277 (9)
C3—H31	0.908	C16—F4	1.3379 (10)
C4—C5	1.3927 (11)	C16—F5	1.3405 (10)
C4—C9	1.3951 (11)	C16—F6	1.3452 (10)
C5—C6	1.3945 (12)	O1—S1	1.4450 (7)
C5—H51	0.913	O2—S1	1.4440 (7)
C6—C7	1.3962 (14)	O3—S1	1.4475 (7)
C6—H61	0.939	O4—S2	1.4437 (7)
C7—C8	1.3946 (13)	O5—S2	1.4480 (8)
C7—H71	0.932	O6—S2	1.4469 (7)
N1—C1—N2	108.10 (7)	N4—C14—H142	108.6
N1—C1—H11	126.1	N4—C14—H143	108.3
N2—C1—H11	125.8	H142—C14—H143	108.6
C3—C2—N1	107.14 (7)	N4—C14—H141	109.1
C3—C2—H21	129.7	H142—C14—H141	112.1
N1—C2—H21	123.2	H143—C14—H141	110.1
C2—C3—N2	106.55 (7)	S1—C15—F1	110.98 (7)
C2—C3—H31	129.0	S1—C15—F2	111.08 (7)
N2—C3—H31	124.4	F1—C15—F2	107.41 (9)
C5—C4—C9	120.16 (7)	S1—C15—F3	111.68 (7)
C5—C4—N2	119.69 (7)	F1—C15—F3	107.90 (9)
N2—C4—C9	120.14 (7)	F2—C15—F3	107.60 (9)
C4—C5—C6	119.21 (8)	S2—C16—F4	112.10 (6)
C4—C5—H51	119.3	S2—C16—F5	111.35 (6)
C6—C5—H51	121.4	F4—C16—F5	107.85 (7)
C5—C6—C7	120.60 (8)	S2—C16—F6	110.60 (6)
C5—C6—H61	121.4	F4—C16—F6	107.42 (7)
C7—C6—H61	118.0	F5—C16—F6	107.31 (7)
C6—C7—C8	119.85 (8)	C13—N1—C2	126.16 (7)
C6—C7—H71	120.6	C13—N1—C1	124.52 (8)
C8—C7—H71	119.6	C2—N1—C1	109.22 (7)
C7—C8—C9	119.53 (8)	C4—N2—C3	126.33 (7)
C7—C8—H81	121.3	C4—N2—C1	124.51 (7)
C9—C8—H81	119.1	C3—N2—C1	108.99 (7)
C4—C9—C8	120.50 (7)	C9—N3—C10	125.83 (7)
N3—C9—C4	120.24 (7)	C9—N3—C12	124.97 (7)
C8—C9—N3	119.24 (7)	C10—N3—C12	109.16 (7)
C11—C10—N3	106.39 (7)	C14—N4—C11	125.70 (8)
C11—C10—H101	131.0	C14—N4—C12	124.87 (8)
N3—C10—H101	122.7	C11—N4—C12	109.39 (7)
C10—C11—N4	107.15 (7)	C15—S1—O3	102.73 (4)
C10—C11—H111	129.2	C15—S1—O1	102.63 (5)
N4—C11—H111	123.6	O3—S1—O1	115.12 (4)
N3—C12—N4	107.91 (7)	C15—S1—O2	103.68 (5)
N3—C12—H121	125.3	O3—S1—O2	114.97 (4)
N4—C12—H121	126.7	O1—S1—O2	115.16 (5)
N1—C13—H132	110.2	C16—S2—O5	103.42 (4)
N1—C13—H131	110.3	C16—S2—O6	103.32 (4)
H132—C13—H131	109.9	O5—S2—O6	114.92 (5)
N1—C13—H133	108.2	C16—S2—O4	102.52 (4)
H132—C13—H133	108.1	O5—S2—O4	115.12 (5)
H131—C13—H133	110.1	O6—S2—O4	115.06 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H21···O5^i	0.93	2.48	3.2692 (12)	142
C3—H31···O6^ii	0.91	2.44	3.2600 (11)	150
C10—H101···O3	0.92	2.48	3.2922 (12)	147
C11—H111···O1^iii	0.91	2.37	3.1827 (12)	148
C12—H121···O5^ii	0.92	2.52	3.3632 (12)	153
C2—H21···F2^iv	0.93	2.81	3.5001 (11)	132
C13—H132···F2^v	0.97	2.67	3.3854 (13)	131
C13—H133···F6^vi	0.98	2.71	3.1440 (11)	107
C14—H141···F6^vii	0.95	2.65	3.3680 (12)	133

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