Bis(2-{[3-methyl-4-(2,2,2-trifluoro­eth­oxy)-2-pyrid­yl]methyl­sulfan­yl}-1H,3H+-benzimidazolium) 2,5-dichloro-3,6-dioxocyclo­hexa-1,4-diene-1,4-diolate

Hakim Al-arique, Q.N.M.; Jasinski, J.P.; Butcher, R.J.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536810019665

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1507-o1508

https://doi.org/10.1107/S1600536810019665

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Bis(2-{[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methylsulfanyl}-1H,3H⁺-benzimidazolium) 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate

Q. N. M. Hakim Al-arique,^a Jerry P. Jasinski,^b ^* Ray J. Butcher,^c H. S. Yathirajan ^a and B. Narayana ^d

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^dDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 11 May 2010; accepted 25 May 2010; online 29 May 2010)

The title salt, 2C₁₆H₁₅F₃N₃OS⁺·C₆Cl₂O₄²⁻, is composed of two independent cations of a lansoprazole {systematic name 2-([3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl]methylsulfinyl)-1H-benzo[d]imidazole} intermediate and a dianion of chloranilic acid. In the cations of the lansoprazole intermediate, the dihedral angles between the least-squares planes of the pyridine and benzimidazole rings are 11.1 (6) and 13.1 (5)°, respectively. The dihedral angles between the mean plane of the benzene ring in the chloranilic acid dianion and the pryidine and benzimidazole rings of the two lansoprazole intermediate groups are 71.8 (1)/80.5 (7) and 74.2 (4)/74.8 (6)°. In addition to ionic bond interactions, the lansoprazole intermediate and chloranilic ions are connected by strong N—H⋯O hydrogen bonds, which produce a set of extended O—H⋯O—H⋯O—H chains along the b axis in the (011) plane. In addition, weak C—H⋯O, C—H⋯F, N—H⋯Cl and π–π [centroid–centroid distances = 3.5631 (15), 3.8187 (13), 3.7434 (17) and 3.842 (2) Å] intermolecular interactions are observed, which contribute to crystal packing stability.

Related literature

For bacterial growth inhibition by lansoprazole and its analogs, see: Iwahi et al. (1991 ). For related structures, see: Arslan et al. (2006 ); Gotoh et al. (2006 , 2007 , 2008 ); Ishida (2004a ,b ,c ); Ishida & Kashino (1999 , 2000 ); Meng & Qian (2006 ); Refat et al. (2006 ); Swamy & Ravikumar (2007 ); Tabuchi et al. (2005 ); Vyas et al. (2000 ).

Experimental

Crystal data

2C₁₆H₁₅F₃N₃OS⁺·C₆Cl₂O₄²⁻
M_r = 915.70
Monoclinic, P 2₁ /n
a = 9.48575 (8) Å
b = 23.6316 (2) Å
c = 17.86775 (15) Å
β = 100.2065 (9)°
V = 3941.92 (6) Å³
Z = 4
Cu Kα radiation
μ = 3.22 mm⁻¹
T = 295 K
0.38 × 0.24 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.692, T_max = 1.000
19572 measured reflections
8269 independent reflections
6572 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.158
S = 1.10
8269 reflections
600 parameters
138 restraints
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O3	0.86	1.95	2.749 (2)	155
N1A—H1AA⋯Cl2	0.86	2.96	3.5169 (18)	125
N2A—H2AA⋯O5ⁱ	0.86	1.91	2.737 (2)	160
N1B—H1BA⋯O2	0.86	1.89	2.717 (2)	160
N2B—H2BA⋯O6ⁱ	0.86	1.96	2.766 (2)	155
C8A—H8AB⋯O5ⁱ	0.97	2.50	3.195 (3)	127
C8B—H8BA⋯O6ⁱ	0.97	2.45	3.289 (3)	145
C6B—H6BA⋯F3AAⁱⁱ	0.93	2.49	3.104 (5)	124
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810019665/bt5269sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019665/bt5269Isup2.hkl

checkCIF report

Comment top

The Lansoprazole intermediate (Systematic name: 2-([[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridinyl]methyl]sulfanyl) -1H-benzimidazole) in this study is a benzimidazole derivative. Lansoprazole, a widely used proton-pump inhibitor, has been reported to have an independent gastroprotective action. Lansoprazole and its analogs inhibit the growth of Helicobacter pylori at concentrations of several micrograms per milliliter (Iwahi et al., 1991) and is widely used for the treatment of acid-related gastric diseases due to their ability to inhibit acid secretio. The crystal structures of lansoprazole (Vyas et al., 2000) and lansoprazole sulphone have been reported (Swamy & Ravikumar, 2007).

Charge transfer complexes of organic species are intensively studied because of their special type of interaction, which is accompanied by transfer of an electron from the donor to the acceptor. Chloranilic acid is a strong dibasic organic acid which exhibits the electron-acceptor properties on one hand and acidic properties leading to formation of hydrogen bonds on the other hand. In the case of stronger bases the proton-transfer hydrogen bonded ion pairs will be formed which is interesting from the point of view of electron transfer reactions in biological systems. Protonation of the donor from acidic acceptors are generally a route for the formation of ion pair adducts. The synthesis and spectroscopic studies of charge transfer complexes between chloranilic acid and some heterocyclic amines in ethanol and amino heterocyclic donors in acteonitrile have been studied. The interaction of the lansoprazole intermediate as an electron donor with chloranilic acid as electron acceptor in this study resulted in the formation of a charge transfer complex of the title compound (I). In view of the importance of lansoprazole, this paper reports the crystal structure of [C₁₆H₁₅F₃N₃OS+]₂ [C₆Cl₂O₄^2-], (I).

The title compound (I) is a salt composed of two independent cations (A & B) of a lansoprazole intermediate, [C₁₆H₁₅F₃N₃OS+]₂, and a dianion [C₆Cl₂O₄^2-] of chloranilic acid, (2:1) in the asymmetric unit (Fig. 1). In each cation (A & B) of the lansoprazole intermediate the dihedral angles between the least squares planes of the pyridine and benzimidazole rings are 11.1 (6)° (A) and 13.1 (5)° (B), respectively. The dihedral angles between the mean plane of the benzene ring in the chloranilic acid dianion and the pryidine and benzimidazole rings of the two lansoprazole intermediate groups are 71.8 (1)° (A), 80.5 (7)° (B) and 74.2 (4)° (A), 74.8 (6)° (B), respectively. The fluorine atoms in both cations are disordered (relative occupancies = 0.361 (5) (A), 0.639 (5) (A) and 0.684 (5) (B), 0.316 (5) (B)). In neutral chloranilic acid, typical C═O and C–O(—H) bond lengths are 1.22 (1)Å and 1.32 (1) Å. For the chloroanilate monoanion C═O and C–O^-, values of 1.24 (2)Å and 1.25 (2) Å have been reported (Gotoh et al., (2007). In (I), we report values of 1.248 (2)Å (C2═O2), 1.248 (2) Å (C5═O5), 1.249 (2) Å (C3–O3^-) and 1.245 (2) Å (C6–O6^-), respectively. In addition to ionic bond interactions, the lansoprazole intermediate and chloranilic acid ions are connected by strong N—H···O hydrogen bonds [N1A···O3 = 2.749 (2) Å; N2A···O5 = 2.737 (2) Å; N1B···O2 = 2.717 (2) Å; N2B···O6 = 2.766 (2) Å] (Fig. 2, Table 1). This produces a set of O—H···O—H···O—H infinite one-dimensional chains along the b axis in the (011) plane. In addition, weak C—H···O, C—H···F, N—H···Cl (Table 1) and π–π (Table 2) intermolecular stacking interactions are observed which contribute to crystal packing stability (Fig. 2).

Related literature top

For bacterial growth inhibition by Lansoprazole and its analogs, see: Iwahi et al. (1991). For related structures, see: Arslan et al. (2006); Gotoh et al. (2006, 2007, 2008); Ishida (2004a,b,c); Ishida & Kashino (1999, 2000); Meng & Qian (2006); Refat et al. (2006); Swamy & Ravikumar (2007); Tabuchi et al. (2005); Vyas et al. (2000).

Experimental top

The title compound was synthesized by adding a saturated solution of chloranilic acid (0.42 g, 2 mmol) in methanol (10 ml) to a solution of the lansoprazole intermediate (0.74 g, 2 mmol) in methanol (10 ml). A red color developed and the solution was allowed to evaporate slowly at room temperature. The red color complex formed was filtered off, washed with diethyl ether and dried under vacuum (Yield: 72.4%). Crystals were grown from a dimethyl formamide solution (m.p.: 441-444 K). Composition (%) found (calculated) for [C₁₆H₁₅F₃N₃OS+]₂ [C₆Cl₂O₄^2-]: C: 49.76 (49.84); H: 3.28 (3.30); N: 9.15 (9.18).

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); 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 top

	Fig. 1. Molecular structure of [C₁₆H₁₅F₃N₃OS+]₂ [C₆Cl₂O₄^2-], showing the atom labeling scheme and 50% probability displacement ellipsoids. Dashed lines indicate strong N—H···O intermolecular interactions within the asymmetric unit. H atoms are presented as small circles of arbitrary radius.
	Fig. 2. Packing diagram of the title compound ,[C₁₆H₁₅F₃N₃OS+]₂ [C₆Cl₂O₄^2-],, viewed down the a axis. Dashed lines indicate strong N—H···O and weak C—H···O, C—H···F intermolecular hydrogen bonds linking the [C₁₆H₁₅F₃N₃OS+]₂ and [C₆Cl₂O₄^2-] ions into an infinite O—H···O—H···O—H chain network along the b axis in the (011) plane.

Bis(2-{[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methylsulfanyl}- 1H,3H⁺-benzimidazolium) 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate top

Crystal data top

2C₁₆H₁₅F₃N₃OS⁺·C₆Cl₂O₄²⁻	F(000) = 1872
M_r = 915.70	D_x = 1.543 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 10683 reflections
a = 9.48575 (8) Å	θ = 4.5–77.4°
b = 23.6316 (2) Å	µ = 3.22 mm⁻¹
c = 17.86775 (15) Å	T = 295 K
β = 100.2065 (9)°	Prism, red-brown
V = 3941.92 (6) Å³	0.38 × 0.24 × 0.19 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	8269 independent reflections
Radiation source: Enhance (Cu) X-ray Source	6572 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 10.5081 pixels mm^-1	θ_max = 77.6°, θ_min = 4.5°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −29→21
T_min = 0.692, T_max = 1.000	l = −21→22
19572 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.1054P)² + 0.2084P] where P = (F_o² + 2F_c²)/3
8269 reflections	(Δ/σ)_max = 0.007
600 parameters	Δρ_max = 0.87 e Å⁻³
138 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

2C₁₆H₁₅F₃N₃OS⁺·C₆Cl₂O₄²⁻	V = 3941.92 (6) Å³
M_r = 915.70	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 9.48575 (8) Å	µ = 3.22 mm⁻¹
b = 23.6316 (2) Å	T = 295 K
c = 17.86775 (15) Å	0.38 × 0.24 × 0.19 mm
β = 100.2065 (9)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	8269 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	6572 reflections with I > 2σ(I)
T_min = 0.692, T_max = 1.000	R_int = 0.019
19572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	138 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.10	Δρ_max = 0.87 e Å⁻³
8269 reflections	Δρ_min = −0.49 e Å⁻³
600 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	−0.02389 (6)	0.28125 (3)	0.75775 (3)	0.06238 (17)
Cl2	0.65326 (6)	0.29242 (4)	0.82221 (3)	0.06540 (18)
O2	0.16831 (17)	0.31643 (8)	0.65093 (9)	0.0562 (4)
O3	0.45465 (16)	0.32221 (7)	0.67875 (8)	0.0499 (4)
O5	0.45948 (16)	0.26157 (7)	0.92935 (8)	0.0487 (3)
O6	0.17567 (16)	0.25255 (8)	0.90012 (9)	0.0518 (4)
C1	0.1616 (2)	0.28648 (9)	0.77553 (11)	0.0401 (4)
C2	0.2306 (2)	0.30329 (8)	0.71610 (11)	0.0387 (4)
C3	0.3966 (2)	0.30515 (8)	0.73206 (11)	0.0380 (4)
C4	0.4674 (2)	0.28877 (9)	0.80369 (11)	0.0410 (4)
C5	0.3979 (2)	0.27343 (8)	0.86360 (10)	0.0372 (4)
C6	0.2333 (2)	0.27039 (8)	0.84730 (11)	0.0368 (4)
S1A	0.76555 (7)	0.36213 (3)	0.55737 (3)	0.05601 (14)
F1A	0.9879 (2)	0.53715 (13)	0.14545 (16)	0.161 (4)	0.361 (5)
F2A	1.1807 (2)	0.50633 (8)	0.2122 (2)	0.105 (2)	0.361 (5)
F3A	1.1443 (3)	0.59488 (7)	0.2010 (3)	0.149 (3)	0.361 (5)
F1AA	1.0095 (2)	0.51401 (8)	0.15374 (14)	0.1149 (16)	0.639 (5)
F2AA	1.21213 (17)	0.52535 (11)	0.2249 (2)	0.153 (2)	0.639 (5)
F3AA	1.0897 (4)	0.59702 (6)	0.1800 (2)	0.216 (3)	0.639 (5)
O1A	0.9921 (3)	0.49361 (8)	0.29873 (12)	0.0721 (5)
N1A	0.68513 (19)	0.27244 (9)	0.63087 (10)	0.0479 (4)
H1AA	0.6338	0.2931	0.6552	0.057*
N2A	0.8291 (2)	0.24764 (8)	0.55373 (10)	0.0469 (4)
H2AA	0.8853	0.2497	0.5210	0.056*
N3A	0.8120 (2)	0.45798 (9)	0.48750 (13)	0.0592 (5)
C1A	0.7631 (2)	0.29124 (10)	0.58035 (11)	0.0450 (5)
C2A	0.7007 (2)	0.21455 (11)	0.63736 (12)	0.0496 (5)
C3A	0.6439 (3)	0.17509 (13)	0.68139 (16)	0.0650 (7)
H3AA	0.5843	0.1858	0.7150	0.078*
C4A	0.6802 (4)	0.11919 (14)	0.67281 (19)	0.0813 (9)
H4AA	0.6447	0.0916	0.7016	0.098*
C5A	0.7691 (4)	0.10301 (14)	0.62188 (19)	0.0781 (8)
H5AA	0.7894	0.0648	0.6169	0.094*
C6A	0.8277 (3)	0.14224 (12)	0.57871 (15)	0.0634 (6)
H6AA	0.8879	0.1315	0.5454	0.076*
C7A	0.7919 (2)	0.19858 (11)	0.58771 (12)	0.0492 (5)
C8A	0.8823 (3)	0.36051 (11)	0.48755 (15)	0.0570 (6)
H8AA	0.9794	0.3513	0.5116	0.068*
H8AB	0.8497	0.3323	0.4490	0.068*
C9A	0.8769 (3)	0.41856 (10)	0.45245 (14)	0.0517 (5)
C10A	0.8074 (3)	0.51054 (12)	0.45988 (16)	0.0653 (7)
H10A	0.7620	0.5382	0.4840	0.078*
C11A	0.8657 (3)	0.52621 (12)	0.39785 (16)	0.0641 (6)
H11A	0.8612	0.5634	0.3807	0.077*
C12A	0.9315 (3)	0.48433 (11)	0.36190 (15)	0.0577 (6)
C13A	0.9393 (3)	0.42859 (10)	0.38825 (14)	0.0526 (5)
C14A	1.0114 (3)	0.38352 (12)	0.34966 (17)	0.0673 (7)
H14A	1.0194	0.3496	0.3797	0.101*
H14B	1.1052	0.3961	0.3442	0.101*
H14C	0.9558	0.3759	0.3004	0.101*
C15A	1.0090 (6)	0.54929 (14)	0.2751 (2)	0.0985 (12)
H15A	1.0667	0.5708	0.3156	0.118*
H15B	0.9165	0.5676	0.2615	0.118*
C16A	1.08337 (16)	0.54588 (6)	0.20623 (10)	0.1085 (15)
S1B	0.37775 (7)	0.35551 (3)	0.47949 (3)	0.05589 (14)
F1B	0.46185 (16)	0.52009 (8)	0.0783 (2)	0.144 (2)	0.684 (5)
F2B	0.68815 (15)	0.52999 (10)	0.10037 (18)	0.1317 (14)	0.684 (5)
F3B	0.5535 (3)	0.60246 (6)	0.08372 (17)	0.1343 (16)	0.684 (5)
F1BB	0.5025 (3)	0.59349 (8)	0.0729 (2)	0.114 (3)	0.316 (5)
F2BB	0.5274 (3)	0.50406 (7)	0.0777 (2)	0.115 (3)	0.316 (5)
F3BB	0.70535 (15)	0.55741 (14)	0.1178 (3)	0.162 (4)	0.316 (5)
O1B	0.5855 (3)	0.50090 (9)	0.22645 (11)	0.0748 (6)
N1B	0.2888 (2)	0.26340 (9)	0.54297 (11)	0.0492 (4)
H1BA	0.2374	0.2835	0.5679	0.059*
N2B	0.4330 (2)	0.24045 (8)	0.46559 (10)	0.0467 (4)
H2BA	0.4892	0.2434	0.4329	0.056*
N3B	0.4174 (3)	0.45403 (9)	0.41534 (12)	0.0618 (5)
C1B	0.3674 (2)	0.28334 (10)	0.49428 (11)	0.0446 (4)
C2B	0.3029 (3)	0.20543 (11)	0.54709 (14)	0.0540 (5)
C3B	0.2441 (4)	0.16568 (14)	0.58983 (19)	0.0760 (8)
H3BA	0.1832	0.1759	0.6230	0.091*
C4B	0.2813 (5)	0.10991 (17)	0.5801 (2)	0.0975 (12)
H4BA	0.2449	0.0817	0.6077	0.117*
C5B	0.3720 (5)	0.09494 (15)	0.5299 (3)	0.0991 (13)
H5BA	0.3935	0.0569	0.5245	0.119*
C6B	0.4311 (4)	0.13501 (13)	0.48792 (18)	0.0744 (8)
H6BA	0.4922	0.1247	0.4549	0.089*
C7B	0.3950 (3)	0.19064 (11)	0.49732 (13)	0.0526 (5)
C8B	0.4554 (3)	0.35551 (11)	0.39369 (13)	0.0556 (6)
H8BA	0.5487	0.3375	0.4032	0.067*
H8BB	0.3941	0.3350	0.3535	0.067*
C9B	0.4691 (3)	0.41622 (10)	0.37107 (12)	0.0495 (5)
C10B	0.4281 (4)	0.50877 (12)	0.39791 (16)	0.0680 (7)
H10B	0.3962	0.5355	0.4293	0.082*
C11B	0.4831 (3)	0.52773 (12)	0.33653 (15)	0.0652 (7)
H11B	0.4876	0.5662	0.3260	0.078*
C12B	0.5319 (3)	0.48743 (11)	0.29059 (13)	0.0566 (6)
C13B	0.5295 (3)	0.43033 (10)	0.30822 (12)	0.0513 (5)
C14B	0.5910 (3)	0.38603 (12)	0.26233 (15)	0.0655 (7)
H14D	0.6283	0.4040	0.2218	0.098*
H14E	0.5171	0.3598	0.2415	0.098*
H14F	0.6667	0.3661	0.2946	0.098*
C15B	0.5554 (4)	0.55470 (13)	0.19478 (18)	0.0803 (9)
H15C	0.6229	0.5822	0.2207	0.096*
H15D	0.4595	0.5663	0.2001	0.096*
C16B	0.56725 (15)	0.55150 (6)	0.11217 (10)	0.0924 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0340 (2)	0.1034 (5)	0.0508 (3)	−0.0013 (2)	0.0106 (2)	0.0039 (3)
Cl2	0.0347 (2)	0.1177 (5)	0.0455 (3)	−0.0089 (3)	0.0117 (2)	0.0020 (3)
O2	0.0479 (8)	0.0864 (11)	0.0365 (7)	0.0193 (8)	0.0130 (6)	0.0129 (7)
O3	0.0493 (7)	0.0665 (9)	0.0389 (7)	−0.0025 (7)	0.0212 (6)	0.0073 (6)
O5	0.0436 (7)	0.0706 (9)	0.0325 (7)	−0.0026 (7)	0.0081 (6)	0.0078 (6)
O6	0.0443 (7)	0.0765 (10)	0.0379 (7)	−0.0111 (7)	0.0164 (6)	0.0072 (7)
C1	0.0313 (8)	0.0535 (10)	0.0374 (9)	−0.0002 (7)	0.0110 (7)	0.0003 (8)
C2	0.0398 (9)	0.0452 (9)	0.0334 (9)	0.0063 (7)	0.0127 (7)	0.0008 (7)
C3	0.0396 (9)	0.0429 (9)	0.0346 (9)	−0.0001 (7)	0.0147 (7)	0.0005 (7)
C4	0.0321 (8)	0.0577 (11)	0.0354 (9)	−0.0044 (8)	0.0117 (7)	0.0010 (8)
C5	0.0382 (9)	0.0430 (9)	0.0320 (8)	−0.0026 (7)	0.0106 (7)	0.0008 (7)
C6	0.0378 (9)	0.0408 (9)	0.0341 (8)	−0.0045 (7)	0.0130 (7)	−0.0013 (7)
S1A	0.0645 (3)	0.0645 (3)	0.0451 (3)	0.0095 (3)	0.0264 (2)	−0.0001 (2)
F1A	0.162 (7)	0.194 (7)	0.125 (6)	−0.033 (6)	0.018 (5)	0.057 (6)
F2A	0.113 (4)	0.084 (3)	0.136 (5)	−0.031 (3)	0.073 (4)	−0.031 (3)
F3A	0.227 (6)	0.088 (4)	0.166 (6)	−0.049 (4)	0.124 (5)	0.007 (4)
F1AA	0.176 (4)	0.110 (3)	0.0567 (18)	0.033 (3)	0.016 (2)	−0.0122 (17)
F2AA	0.109 (3)	0.207 (5)	0.149 (4)	−0.066 (3)	0.042 (3)	−0.009 (4)
F3AA	0.442 (8)	0.104 (4)	0.136 (4)	−0.017 (5)	0.142 (5)	0.011 (3)
O1A	0.0979 (14)	0.0607 (10)	0.0668 (11)	−0.0055 (10)	0.0391 (10)	0.0041 (9)
N1A	0.0432 (9)	0.0682 (11)	0.0350 (8)	−0.0004 (8)	0.0144 (7)	−0.0060 (8)
N2A	0.0453 (8)	0.0673 (11)	0.0309 (8)	0.0023 (8)	0.0142 (7)	−0.0026 (7)
N3A	0.0671 (12)	0.0609 (11)	0.0552 (11)	0.0049 (10)	0.0261 (9)	−0.0069 (9)
C1A	0.0412 (9)	0.0653 (12)	0.0298 (8)	0.0003 (9)	0.0097 (7)	−0.0036 (8)
C2A	0.0472 (11)	0.0671 (13)	0.0361 (10)	−0.0062 (9)	0.0119 (8)	−0.0051 (9)
C3A	0.0706 (15)	0.0759 (16)	0.0553 (13)	−0.0119 (13)	0.0301 (12)	−0.0056 (12)
C4A	0.107 (2)	0.0754 (18)	0.0710 (18)	−0.0169 (17)	0.0404 (17)	−0.0002 (15)
C5A	0.101 (2)	0.0652 (16)	0.0752 (18)	−0.0023 (15)	0.0363 (17)	−0.0048 (14)
C6A	0.0743 (16)	0.0688 (15)	0.0511 (13)	0.0052 (12)	0.0219 (12)	−0.0066 (11)
C7A	0.0501 (11)	0.0659 (13)	0.0330 (9)	−0.0028 (10)	0.0108 (8)	−0.0056 (9)
C8A	0.0640 (13)	0.0591 (13)	0.0554 (13)	0.0039 (11)	0.0313 (11)	−0.0038 (10)
C9A	0.0541 (11)	0.0573 (12)	0.0470 (11)	0.0001 (10)	0.0180 (9)	−0.0068 (9)
C10A	0.0741 (16)	0.0620 (14)	0.0636 (15)	0.0097 (12)	0.0230 (13)	−0.0104 (12)
C11A	0.0773 (16)	0.0535 (13)	0.0636 (15)	0.0023 (12)	0.0186 (13)	−0.0012 (11)
C12A	0.0625 (13)	0.0615 (13)	0.0522 (12)	−0.0056 (11)	0.0192 (10)	−0.0022 (10)
C13A	0.0557 (12)	0.0576 (12)	0.0488 (11)	−0.0010 (10)	0.0208 (10)	−0.0052 (10)
C14A	0.0813 (16)	0.0654 (15)	0.0651 (15)	0.0067 (13)	0.0399 (13)	−0.0019 (12)
C15A	0.162 (4)	0.0620 (17)	0.083 (2)	−0.012 (2)	0.054 (2)	0.0002 (16)
C16A	0.184 (5)	0.072 (2)	0.076 (2)	−0.025 (3)	0.040 (3)	0.0107 (18)
S1B	0.0684 (3)	0.0580 (3)	0.0482 (3)	0.0082 (3)	0.0293 (2)	0.0006 (2)
F1B	0.211 (5)	0.118 (3)	0.091 (3)	−0.007 (3)	−0.006 (3)	−0.012 (2)
F2B	0.191 (3)	0.118 (3)	0.117 (2)	0.027 (3)	0.110 (2)	0.008 (2)
F3B	0.265 (5)	0.0703 (18)	0.091 (2)	0.014 (2)	0.094 (3)	0.0221 (16)
F1BB	0.135 (6)	0.123 (6)	0.083 (5)	0.006 (5)	0.017 (4)	0.047 (4)
F2BB	0.188 (7)	0.108 (5)	0.053 (3)	0.038 (5)	0.028 (4)	−0.009 (3)
F3BB	0.150 (7)	0.205 (9)	0.149 (7)	−0.009 (6)	0.076 (6)	0.030 (7)
O1B	0.1124 (15)	0.0664 (11)	0.0570 (10)	0.0159 (11)	0.0467 (10)	0.0109 (8)
N1B	0.0446 (9)	0.0646 (11)	0.0415 (9)	0.0019 (8)	0.0158 (7)	−0.0003 (8)
N2B	0.0459 (9)	0.0610 (10)	0.0353 (8)	0.0045 (8)	0.0124 (7)	−0.0030 (7)
N3B	0.0853 (14)	0.0589 (11)	0.0494 (10)	0.0164 (10)	0.0340 (10)	0.0038 (9)
C1B	0.0416 (9)	0.0599 (12)	0.0332 (9)	0.0020 (8)	0.0088 (7)	−0.0019 (8)
C2B	0.0521 (12)	0.0662 (14)	0.0443 (11)	−0.0036 (10)	0.0103 (9)	−0.0003 (10)
C3B	0.0829 (18)	0.0791 (18)	0.0714 (18)	−0.0151 (15)	0.0283 (15)	0.0081 (15)
C4B	0.123 (3)	0.079 (2)	0.096 (3)	−0.018 (2)	0.036 (2)	0.0131 (19)
C5B	0.143 (4)	0.0581 (17)	0.097 (3)	0.000 (2)	0.024 (3)	0.0009 (17)
C6B	0.094 (2)	0.0654 (16)	0.0653 (17)	0.0083 (15)	0.0192 (15)	−0.0082 (13)
C7B	0.0550 (12)	0.0615 (13)	0.0408 (11)	0.0016 (10)	0.0071 (9)	−0.0021 (9)
C8B	0.0700 (14)	0.0589 (13)	0.0435 (11)	0.0150 (11)	0.0257 (10)	0.0054 (9)
C9B	0.0563 (11)	0.0569 (12)	0.0378 (10)	0.0129 (10)	0.0151 (9)	0.0019 (9)
C10B	0.0955 (18)	0.0612 (14)	0.0562 (13)	0.0193 (13)	0.0377 (13)	−0.0011 (11)
C11B	0.0927 (19)	0.0547 (13)	0.0548 (13)	0.0128 (13)	0.0310 (13)	0.0052 (11)
C12B	0.0704 (14)	0.0635 (13)	0.0404 (11)	0.0083 (11)	0.0223 (10)	0.0047 (10)
C13B	0.0613 (12)	0.0585 (12)	0.0363 (10)	0.0128 (10)	0.0148 (9)	0.0012 (9)
C14B	0.0878 (17)	0.0666 (15)	0.0495 (12)	0.0172 (13)	0.0321 (12)	−0.0007 (11)
C15B	0.129 (3)	0.0583 (15)	0.0645 (16)	−0.0002 (16)	0.0478 (17)	0.0028 (12)
C16B	0.148 (3)	0.0671 (18)	0.075 (2)	0.002 (2)	0.054 (2)	0.0131 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.7363 (19)	C14A—H14A	0.9600
Cl2—C4	1.7370 (19)	C14A—H14B	0.9600
O2—C2	1.248 (2)	C14A—H14C	0.9600
O3—C3	1.249 (2)	C15A—C16A	1.525 (4)
O5—C5	1.248 (2)	C15A—H15A	0.9700
O6—C6	1.245 (2)	C15A—H15B	0.9700
C1—C6	1.394 (3)	S1B—C1B	1.731 (2)
C1—C2	1.400 (3)	S1B—C8B	1.814 (2)
C2—C3	1.551 (3)	F1B—C16B	1.3048 (11)
C3—C4	1.391 (3)	F2B—C16B	1.3053 (11)
C4—C5	1.401 (3)	F3B—C16B	1.3047 (11)
C5—C6	1.539 (3)	F1BB—C16B	1.3039 (12)
S1A—C1A	1.726 (2)	F2BB—C16B	1.3026 (12)
S1A—C8A	1.809 (2)	F3BB—C16B	1.3034 (11)
F1A—C16A	1.3016 (12)	O1B—C12B	1.371 (3)
F2A—C16A	1.3045 (11)	O1B—C15B	1.400 (4)
F3A—C16A	1.3052 (12)	N1B—C1B	1.328 (3)
F1AA—C16A	1.3056 (11)	N1B—C2B	1.377 (3)
F2AA—C16A	1.3016 (11)	N1B—H1BA	0.8600
F3AA—C16A	1.3014 (12)	N2B—C1B	1.338 (3)
O1A—C12A	1.372 (3)	N2B—C7B	1.382 (3)
O1A—C15A	1.400 (4)	N2B—H2BA	0.8600
N1A—C1A	1.340 (3)	N3B—C10B	1.339 (4)
N1A—C2A	1.379 (3)	N3B—C9B	1.342 (3)
N1A—H1AA	0.8600	C2B—C3B	1.389 (4)
N2A—C1A	1.336 (3)	C2B—C7B	1.397 (3)
N2A—C7A	1.383 (3)	C3B—C4B	1.383 (5)
N2A—H2AA	0.8600	C3B—H3BA	0.9300
N3A—C9A	1.332 (3)	C4B—C5B	1.393 (6)
N3A—C10A	1.334 (4)	C4B—H4BA	0.9300
C2A—C3A	1.389 (4)	C5B—C6B	1.387 (5)
C2A—C7A	1.397 (3)	C5B—H5BA	0.9300
C3A—C4A	1.381 (5)	C6B—C7B	1.376 (4)
C3A—H3AA	0.9300	C6B—H6BA	0.9300
C4A—C5A	1.399 (4)	C8B—C9B	1.502 (3)
C4A—H4AA	0.9300	C8B—H8BA	0.9700
C5A—C6A	1.384 (4)	C8B—H8BB	0.9700
C5A—H5AA	0.9300	C9B—C13B	1.389 (3)
C6A—C7A	1.390 (4)	C10B—C11B	1.371 (4)
C6A—H6AA	0.9300	C10B—H10B	0.9300
C8A—C9A	1.505 (4)	C11B—C12B	1.389 (3)
C8A—H8AA	0.9700	C11B—H11B	0.9300
C8A—H8AB	0.9700	C12B—C13B	1.387 (4)
C9A—C13A	1.401 (3)	C13B—C14B	1.509 (3)
C10A—C11A	1.374 (4)	C14B—H14D	0.9600
C10A—H10A	0.9300	C14B—H14E	0.9600
C11A—C12A	1.387 (4)	C14B—H14F	0.9600
C11A—H11A	0.9300	C15B—C16B	1.502 (3)
C12A—C13A	1.396 (4)	C15B—H15C	0.9700
C13A—C14A	1.498 (3)	C15B—H15D	0.9700

C6—C1—C2	123.92 (18)	F2AA—C16A—F1AA	109.21 (12)
C6—C1—Cl1	117.53 (15)	F2A—C16A—F1AA	85.83 (17)
C2—C1—Cl1	118.44 (15)	F3A—C16A—F1AA	130.4 (2)
O2—C2—C1	124.80 (18)	F3AA—C16A—C15A	107.4 (2)
O2—C2—C3	117.51 (17)	F2AA—C16A—C15A	111.1 (3)
C1—C2—C3	117.69 (17)	F1A—C16A—C15A	109.2 (3)
O3—C3—C4	125.85 (18)	F2A—C16A—C15A	113.2 (3)
O3—C3—C2	116.08 (17)	F3A—C16A—C15A	106.6 (3)
C4—C3—C2	118.06 (16)	F1AA—C16A—C15A	110.1 (2)
C3—C4—C5	124.00 (18)	C1B—S1B—C8B	99.87 (11)
C3—C4—Cl2	118.02 (14)	C12B—O1B—C15B	118.0 (2)
C5—C4—Cl2	117.81 (15)	C1B—N1B—C2B	109.11 (19)
O5—C5—C4	124.93 (18)	C1B—N1B—H1BA	125.4
O5—C5—C6	117.24 (16)	C2B—N1B—H1BA	125.4
C4—C5—C6	117.83 (16)	C1B—N2B—C7B	108.40 (19)
O6—C6—C1	125.59 (18)	C1B—N2B—H2BA	125.8
O6—C6—C5	116.07 (17)	C7B—N2B—H2BA	125.8
C1—C6—C5	118.34 (16)	C10B—N3B—C9B	117.1 (2)
C1A—S1A—C8A	100.32 (11)	N1B—C1B—N2B	109.6 (2)
C12A—O1A—C15A	119.0 (2)	N1B—C1B—S1B	120.19 (17)
C1A—N1A—C2A	108.78 (19)	N2B—C1B—S1B	130.18 (17)
C1A—N1A—H1AA	125.6	N1B—C2B—C3B	131.1 (3)
C2A—N1A—H1AA	125.6	N1B—C2B—C7B	106.3 (2)
C1A—N2A—C7A	108.54 (18)	C3B—C2B—C7B	122.6 (3)
C1A—N2A—H2AA	125.7	C4B—C3B—C2B	116.0 (3)
C7A—N2A—H2AA	125.7	C4B—C3B—H3BA	122.0
C9A—N3A—C10A	117.7 (2)	C2B—C3B—H3BA	122.0
N2A—C1A—N1A	109.5 (2)	C3B—C4B—C5B	121.5 (3)
N2A—C1A—S1A	129.56 (16)	C3B—C4B—H4BA	119.2
N1A—C1A—S1A	120.94 (17)	C5B—C4B—H4BA	119.2
N1A—C2A—C3A	131.9 (2)	C6B—C5B—C4B	122.0 (3)
N1A—C2A—C7A	106.5 (2)	C6B—C5B—H5BA	119.0
C3A—C2A—C7A	121.6 (2)	C4B—C5B—H5BA	119.0
C4A—C3A—C2A	116.7 (3)	C7B—C6B—C5B	117.0 (3)
C4A—C3A—H3AA	121.6	C7B—C6B—H6BA	121.5
C2A—C3A—H3AA	121.6	C5B—C6B—H6BA	121.5
C3A—C4A—C5A	121.7 (3)	C6B—C7B—N2B	132.5 (3)
C3A—C4A—H4AA	119.2	C6B—C7B—C2B	120.9 (3)
C5A—C4A—H4AA	119.2	N2B—C7B—C2B	106.6 (2)
C6A—C5A—C4A	121.8 (3)	C9B—C8B—S1B	107.15 (16)
C6A—C5A—H5AA	119.1	C9B—C8B—H8BA	110.3
C4A—C5A—H5AA	119.1	S1B—C8B—H8BA	110.3
C5A—C6A—C7A	116.5 (3)	C9B—C8B—H8BB	110.3
C5A—C6A—H6AA	121.7	S1B—C8B—H8BB	110.3
C7A—C6A—H6AA	121.7	H8BA—C8B—H8BB	108.5
N2A—C7A—C6A	131.7 (2)	N3B—C9B—C13B	124.2 (2)
N2A—C7A—C2A	106.7 (2)	N3B—C9B—C8B	114.8 (2)
C6A—C7A—C2A	121.6 (2)	C13B—C9B—C8B	121.0 (2)
C9A—C8A—S1A	106.77 (16)	N3B—C10B—C11B	123.8 (2)
C9A—C8A—H8AA	110.4	N3B—C10B—H10B	118.1
S1A—C8A—H8AA	110.4	C11B—C10B—H10B	118.1
C9A—C8A—H8AB	110.4	C10B—C11B—C12B	117.6 (2)
S1A—C8A—H8AB	110.4	C10B—C11B—H11B	121.2
H8AA—C8A—H8AB	108.6	C12B—C11B—H11B	121.2
N3A—C9A—C13A	124.3 (2)	O1B—C12B—C13B	116.0 (2)
N3A—C9A—C8A	115.2 (2)	O1B—C12B—C11B	123.1 (2)
C13A—C9A—C8A	120.5 (2)	C13B—C12B—C11B	120.8 (2)
N3A—C10A—C11A	123.9 (2)	C12B—C13B—C9B	116.3 (2)
N3A—C10A—H10A	118.1	C12B—C13B—C14B	121.9 (2)
C11A—C10A—H10A	118.1	C9B—C13B—C14B	121.8 (2)
C10A—C11A—C12A	117.4 (3)	C13B—C14B—H14D	109.5
C10A—C11A—H11A	121.3	C13B—C14B—H14E	109.5
C12A—C11A—H11A	121.3	H14D—C14B—H14E	109.5
O1A—C12A—C11A	123.7 (2)	C13B—C14B—H14F	109.5
O1A—C12A—C13A	115.0 (2)	H14D—C14B—H14F	109.5
C11A—C12A—C13A	121.2 (2)	H14E—C14B—H14F	109.5
C12A—C13A—C9A	115.5 (2)	O1B—C15B—C16B	107.8 (2)
C12A—C13A—C14A	121.1 (2)	O1B—C15B—H15C	110.1
C9A—C13A—C14A	123.4 (2)	C16B—C15B—H15C	110.1
C13A—C14A—H14A	109.5	O1B—C15B—H15D	110.1
C13A—C14A—H14B	109.5	C16B—C15B—H15D	110.1
H14A—C14A—H14B	109.5	H15C—C15B—H15D	108.5
C13A—C14A—H14C	109.5	F2BB—C16B—F3BB	109.42 (13)
H14A—C14A—H14C	109.5	F2BB—C16B—F1BB	109.35 (13)
H14B—C14A—H14C	109.5	F3BB—C16B—F1BB	109.33 (13)
O1A—C15A—C16A	106.7 (3)	F2BB—C16B—F3B	127.6 (2)
O1A—C15A—H15A	110.4	F3BB—C16B—F3B	87.8 (2)
C16A—C15A—H15A	110.4	F3BB—C16B—F1B	140.7 (2)
O1A—C15A—H15B	110.4	F1BB—C16B—F1B	86.25 (16)
C16A—C15A—H15B	110.4	F3B—C16B—F1B	109.20 (12)
H15A—C15A—H15B	108.6	F2BB—C16B—F2B	77.19 (18)
F3AA—C16A—F2AA	109.73 (12)	F1BB—C16B—F2B	123.6 (2)
F3AA—C16A—F1A	85.21 (19)	F3B—C16B—F2B	109.08 (12)
F2AA—C16A—F1A	129.6 (2)	F1B—C16B—F2B	109.06 (12)
F3AA—C16A—F2A	128.2 (2)	F2BB—C16B—C15B	116.2 (3)
F1A—C16A—F2A	109.42 (12)	F3BB—C16B—C15B	99.7 (3)
F2AA—C16A—F3A	86.66 (18)	F1BB—C16B—C15B	112.3 (3)
F1A—C16A—F3A	109.40 (13)	F3B—C16B—C15B	108.5 (2)
F2A—C16A—F3A	109.00 (12)	F1B—C16B—C15B	107.4 (2)
F3AA—C16A—F1AA	109.29 (12)	F2B—C16B—C15B	113.5 (2)

C6—C1—C2—O2	178.1 (2)	C11A—C12A—C13A—C14A	−179.5 (3)
Cl1—C1—C2—O2	2.0 (3)	N3A—C9A—C13A—C12A	0.7 (4)
C6—C1—C2—C3	−1.3 (3)	C8A—C9A—C13A—C12A	−178.2 (2)
Cl1—C1—C2—C3	−177.35 (14)	N3A—C9A—C13A—C14A	−179.9 (3)
O2—C2—C3—O3	3.1 (3)	C8A—C9A—C13A—C14A	1.2 (4)
C1—C2—C3—O3	−177.56 (19)	C12A—O1A—C15A—C16A	177.9 (2)
O2—C2—C3—C4	−177.9 (2)	O1A—C15A—C16A—F3AA	175.1 (3)
C1—C2—C3—C4	1.5 (3)	O1A—C15A—C16A—F2AA	−64.9 (4)
O3—C3—C4—C5	175.6 (2)	O1A—C15A—C16A—F1A	84.2 (4)
C2—C3—C4—C5	−3.4 (3)	O1A—C15A—C16A—F2A	−38.0 (4)
O3—C3—C4—Cl2	0.4 (3)	O1A—C15A—C16A—F3A	−157.8 (3)
C2—C3—C4—Cl2	−178.54 (14)	O1A—C15A—C16A—F1AA	56.2 (4)
C3—C4—C5—O5	−175.9 (2)	C2B—N1B—C1B—N2B	0.2 (3)
Cl2—C4—C5—O5	−0.8 (3)	C2B—N1B—C1B—S1B	−177.41 (16)
C3—C4—C5—C6	4.6 (3)	C7B—N2B—C1B—N1B	−0.1 (2)
Cl2—C4—C5—C6	179.79 (14)	C7B—N2B—C1B—S1B	177.27 (18)
C2—C1—C6—O6	−176.2 (2)	C8B—S1B—C1B—N1B	−165.94 (18)
Cl1—C1—C6—O6	−0.1 (3)	C8B—S1B—C1B—N2B	17.0 (2)
C2—C1—C6—C5	2.5 (3)	C1B—N1B—C2B—C3B	179.3 (3)
Cl1—C1—C6—C5	178.64 (14)	C1B—N1B—C2B—C7B	−0.3 (3)
O5—C5—C6—O6	−4.7 (3)	N1B—C2B—C3B—C4B	−180.0 (3)
C4—C5—C6—O6	174.79 (19)	C7B—C2B—C3B—C4B	−0.3 (5)
O5—C5—C6—C1	176.48 (19)	C2B—C3B—C4B—C5B	−0.3 (6)
C4—C5—C6—C1	−4.0 (3)	C3B—C4B—C5B—C6B	0.8 (7)
C7A—N2A—C1A—N1A	0.5 (2)	C4B—C5B—C6B—C7B	−0.6 (6)
C7A—N2A—C1A—S1A	−178.46 (17)	C5B—C6B—C7B—N2B	179.9 (3)
C2A—N1A—C1A—N2A	−0.1 (2)	C5B—C6B—C7B—C2B	0.0 (5)
C2A—N1A—C1A—S1A	178.96 (15)	C1B—N2B—C7B—C6B	179.9 (3)
C8A—S1A—C1A—N2A	0.0 (2)	C1B—N2B—C7B—C2B	−0.1 (3)
C8A—S1A—C1A—N1A	−178.86 (18)	N1B—C2B—C7B—C6B	−179.8 (2)
C1A—N1A—C2A—C3A	179.8 (3)	C3B—C2B—C7B—C6B	0.5 (4)
C1A—N1A—C2A—C7A	−0.3 (2)	N1B—C2B—C7B—N2B	0.3 (3)
N1A—C2A—C3A—C4A	178.8 (3)	C3B—C2B—C7B—N2B	−179.4 (3)
C7A—C2A—C3A—C4A	−1.0 (4)	C1B—S1B—C8B—C9B	178.68 (17)
C2A—C3A—C4A—C5A	−0.4 (5)	C10B—N3B—C9B—C13B	−1.3 (4)
C3A—C4A—C5A—C6A	1.4 (6)	C10B—N3B—C9B—C8B	179.5 (3)
C4A—C5A—C6A—C7A	−0.9 (5)	S1B—C8B—C9B—N3B	−2.7 (3)
C1A—N2A—C7A—C6A	178.2 (3)	S1B—C8B—C9B—C13B	178.04 (19)
C1A—N2A—C7A—C2A	−0.7 (2)	C9B—N3B—C10B—C11B	2.5 (5)
C5A—C6A—C7A—N2A	−179.2 (3)	N3B—C10B—C11B—C12B	−0.8 (5)
C5A—C6A—C7A—C2A	−0.5 (4)	C15B—O1B—C12B—C13B	163.0 (3)
N1A—C2A—C7A—N2A	0.6 (2)	C15B—O1B—C12B—C11B	−17.4 (4)
C3A—C2A—C7A—N2A	−179.5 (2)	C10B—C11B—C12B—O1B	178.1 (3)
N1A—C2A—C7A—C6A	−178.4 (2)	C10B—C11B—C12B—C13B	−2.4 (5)
C3A—C2A—C7A—C6A	1.5 (4)	O1B—C12B—C13B—C9B	−177.0 (2)
C1A—S1A—C8A—C9A	171.22 (17)	C11B—C12B—C13B—C9B	3.4 (4)
C10A—N3A—C9A—C13A	−0.6 (4)	O1B—C12B—C13B—C14B	3.7 (4)
C10A—N3A—C9A—C8A	178.4 (2)	C11B—C12B—C13B—C14B	−175.8 (3)
S1A—C8A—C9A—N3A	10.6 (3)	N3B—C9B—C13B—C12B	−1.6 (4)
S1A—C8A—C9A—C13A	−170.4 (2)	C8B—C9B—C13B—C12B	177.5 (2)
C9A—N3A—C10A—C11A	−0.2 (4)	N3B—C9B—C13B—C14B	177.6 (3)
N3A—C10A—C11A—C12A	0.8 (5)	C8B—C9B—C13B—C14B	−3.3 (4)
C15A—O1A—C12A—C11A	10.1 (5)	C12B—O1B—C15B—C16B	−156.3 (2)
C15A—O1A—C12A—C13A	−170.4 (3)	O1B—C15B—C16B—F2BB	34.4 (4)
C10A—C11A—C12A—O1A	178.9 (3)	O1B—C15B—C16B—F3BB	−82.9 (3)
C10A—C11A—C12A—C13A	−0.6 (4)	O1B—C15B—C16B—F1BB	161.4 (2)
O1A—C12A—C13A—C9A	−179.6 (2)	O1B—C15B—C16B—F3B	−173.8 (2)
C11A—C12A—C13A—C9A	−0.1 (4)	O1B—C15B—C16B—F1B	68.3 (3)
O1A—C12A—C13A—C14A	0.9 (4)	O1B—C15B—C16B—F2B	−52.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O3	0.86	1.95	2.749 (2)	155
N1A—H1AA···Cl2	0.86	2.96	3.5169 (18)	125
N2A—H2AA···O5ⁱ	0.86	1.91	2.737 (2)	160
N1B—H1BA···O2	0.86	1.89	2.717 (2)	160
N2B—H2BA···O6ⁱ	0.86	1.96	2.766 (2)	155
C8A—H8AB···O5ⁱ	0.97	2.50	3.195 (3)	127
C8B—H8BA···O6ⁱ	0.97	2.45	3.289 (3)	145
C6B—H6BA···F3AAⁱⁱ	0.93	2.49	3.104 (5)	124

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

Experimental details

Crystal data
Chemical formula	2C₁₆H₁₅F₃N₃OS⁺·C₆Cl₂O₄²⁻
M_r	915.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	9.48575 (8), 23.6316 (2), 17.86775 (15)
β (°)	100.2065 (9)
V (Å³)	3941.92 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.22
Crystal size (mm)	0.38 × 0.24 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.692, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19572, 8269, 6572
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.158, 1.10
No. of reflections	8269
No. of parameters	600
No. of restraints	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.49

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O3	0.86	1.95	2.749 (2)	154.6
N1A—H1AA···Cl2	0.86	2.96	3.5169 (18)	124.6
N2A—H2AA···O5ⁱ	0.86	1.91	2.737 (2)	160.3
N1B—H1BA···O2	0.86	1.89	2.717 (2)	160.2
N2B—H2BA···O6ⁱ	0.86	1.96	2.766 (2)	155.1
C8A—H8AB···O5ⁱ	0.97	2.50	3.195 (3)	127.1
C8B—H8BA···O6ⁱ	0.97	2.45	3.289 (3)	144.6
C6B—H6BA···F3AAⁱⁱ	0.93	2.49	3.104 (5)	124.2

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

Weak π-π hydrogen-bond intermoleular interactions (Å) top

Cg···Cg	D···A
Cg1···Cg4ⁱ	3.8187 (13)
Cg2···Cg2ⁱⁱ	3.5631 (15)
Cg2···Cg5ⁱ	3.7434 (17)
Cg3···Cg6ⁱ	3.842 (2)

Symmetry codes: (i) x, y, z; (ii) 2-x, 1-y, 1-z; Cg1,Cg2,Cg3,Cg4,Cg5,Cg6 are the centroids of the N1A/C1A/N2A/C7A/C2A; N3A/C9A/C13A/C12A/C11A/C10A; C2A–C7A; N1B/C1B/N2B/C7B/C2B; N3B/C9B/C13B/C12B/C11B/C10B; C2B–C7B rings.

Acknowledgements

QNMHA thanks the University of Mysore for use of their research facilities and HSY thanks the University of Mysore for a sabbatical. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

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