4,4′-Oxybis(2,6-di­methyl­pyridinium) bis­(tri­fluoro­methane­sulfonate)

In the asymmetric unit of the title salt, C₁₄H₁₈N₂O²⁺·2CF₃O₃S⁻, the components are linked by two N—H...O and one C—H...O hydrogen bonds. The dipyridinium salt demonstrates a skew conformation based upon C—O—C—C torsion angles of 61.5 (3) and 15.1 (4)°. A C—O—C angle of 119.3 (2)° and C—O bond distances of 1.364 (3) and 1.389 (3) Å are consistent with other dipyridyl ethers. The planes of the pyridyl rings exhibit a twist angle of 67.89 (8)°. One of the tri­fluoro­methane­sulfonate ions shows disorder of the F atoms [in a 0.52 (7):0.48 (7) occupancy ratio] and an O atom [0.64 (8):0.36 (8) occupancy ratio]. In the crystal, the components are linked by C—H...O inter­actions, which form chains along [101].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.049
• wR factor = 0.125
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT214_ALERT_2_B Atom F1      (Anion/Solvent) ADP max/min Ratio          5.7 prolat
PLAT214_ALERT_2_B Atom F2      (Anion/Solvent) ADP max/min Ratio          5.7 prolat
PLAT214_ALERT_2_B Atom F3      (Anion/Solvent) ADP max/min Ratio          5.7 prolat
PLAT214_ALERT_2_B Atom F1'     (Anion/Solvent) ADP max/min Ratio          5.7 prolat
PLAT214_ALERT_2_B Atom F2'     (Anion/Solvent) ADP max/min Ratio          5.7 prolat
PLAT214_ALERT_2_B Atom F3'     (Anion/Solvent) ADP max/min Ratio          5.7 prolat

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          S1 Check
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        3.6 Note
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.7 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0043 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6 Why ?

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT231_ALERT_4_G Hirshfeld Test (Solvent)   S1     --  C15     ..        6.0 su
PLAT231_ALERT_4_G Hirshfeld Test (Solvent)   F1     --  C15     ..        8.0 su
PLAT231_ALERT_4_G Hirshfeld Test (Solvent)   F3     --  C15     ..        8.3 su
PLAT244_ALERT_4_G Low   'Solvent' Ueq as Compared to Neighbors of         C16 Check
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =         25 Note
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              C F3 O3 S
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         53 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   6 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The structures of bridged diaryls have been examined for many years and here we submit another structure into this data set. Based upon dissimilar C–O–C–C torsion angles of 61.5 (3)° and 15.1 (4)°, this structure exhibits a skew conformation (van der Heijden et al. 1975). The previously reported structures of 4,4'-oxybisdipyridyls and their cations (Dunne et al. 1996, Maas, 1985, Constable et al., 1995) have shown a twist structure, with torsion angles that are closer in size. Otherwise, the C–O–C angle of 119.3 (2)° and C–O bond distances of 1.364 (3) Å and 1.389 (3) Å are consistent with reported dipyridyl ethers

The structure of the title salt is shown in Figure 1. N–H···O hydrogen bonds between the dication and the two anions are seen between N1–H1N···O4 and N2–H2N···O7. There are no π-π interactions between pyridinium rings of the dications observed. One of the trifluoromethanesulfonate ions shows a disorder at the fluorines with a 52.0:48.0 percentage distribution and at one oxygen with a 64:36 percentage distribution.

Related literature

For the structure of the unsubstituted 4,4'-oxybisdipyridine, see: Dunne et al. (1996). For the structure of bis[4'-(2,2':6',2"-terpyridinyl)]ether, see: Constable et al. (1995). For the stuctures of the neutral ether 9,9'-oxybisacridine and its dication, see: Maas (1985). For a description of conformations in bridged diphenyls, see: van der Heijden et al. (1975).

S2. Experimental

Colorless crystals of the title compound formed from the slow decomposition of neat 2,6-dimethyl-4-triflatopyridine.

S3. Refinement

All non-hydrogen atoms were refined anisotropically by full matrix least squares on F². Fluorine atoms F1, F2, and F3 were disordered over two positions (52.0/48.0) and were refined anisotropically with similar distances and amplitudes using SADI restraints and EADP constraints. Oxygen atom O2 was found to be disordered over two sites (63.5/36.5) and was refined with DFIX restraints for S–O bond length of 1.44(0.01) Å and O–O distances of 2.41(0.02) Å and ISOR restraint for O2 and O2'. Hydrogen atoms H1N and H2N were found from a Fourier difference map and were refined isotropically with N—H distance of 0.87 (2) Å and 1.20 U_eq of parent N atom. All other hydrogen atoms were placed in calculated positions with appropriate carbon hydrogen bond lengths; C—H(Ar) 0.950 Å and CH₃ 0.980 Å and 1.20 and 1.50 U_eq of parent C atom.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 the title compound, showing the atom labeling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms are presented as spheres of arbitrary radius. Hydrogen bonding is shown with dashed lines.

4,4'-Oxybis(2,6-dimethylpyridinium) bis(trifluoromethanesulfonate)

Crystal data

C14H18N2O^2+·2CF3O3S^−	F(000) = 1080
Mr = 528.44	Dx = 1.585 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5851 reflections
a = 12.7397 (18) Å	θ = 2.4–26.2°
b = 11.3610 (16) Å	µ = 0.33 mm^−1
c = 15.611 (2) Å	T = 100 K
β = 101.405 (4)°	Block, colourless
V = 2214.8 (6) Å^3	0.24 × 0.18 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	4360 independent reflections
Radiation source: fine-focus sealed tube	3546 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→15
Tmin = 0.925, Tmax = 0.968	k = −14→10
15390 measured reflections	l = −19→19

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0486P)^2 + 3.6577P] where P = (Fo^2 + 2Fc^2)/3
4360 reflections	(Δ/σ)max = 0.023
316 parameters	Δρmax = 0.94 e Å^−3
53 restraints	Δρmin = −1.04 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	Occ. (<1)
S1	0.30074 (6)	0.21804 (7)	0.30451 (5)	0.0244 (2)
S2	1.28559 (6)	0.28663 (8)	0.84123 (5)	0.0261 (2)
F1	0.2582 (5)	−0.0159 (3)	0.3316 (4)	0.0595 (7)	0.520 (7)
F2	0.3592 (5)	0.0635 (5)	0.4423 (4)	0.0595 (7)	0.520 (7)
F3	0.1942 (4)	0.1172 (5)	0.4014 (4)	0.0595 (7)	0.520 (7)
F1'	0.2686 (5)	0.0044 (4)	0.3063 (4)	0.0595 (7)	0.480 (7)
F2'	0.3863 (4)	0.0710 (5)	0.4133 (4)	0.0595 (7)	0.480 (7)
F3'	0.2151 (5)	0.0891 (5)	0.4199 (3)	0.0595 (7)	0.480 (7)
F4	1.45831 (17)	0.3944 (2)	0.92267 (16)	0.0540 (7)
F5	1.33893 (18)	0.36761 (19)	1.00127 (13)	0.0429 (6)
F6	1.3158 (2)	0.5016 (2)	0.90176 (19)	0.0642 (8)
O1	0.81802 (15)	0.55937 (18)	0.51520 (13)	0.0198 (5)
O2	0.3883 (10)	0.178 (3)	0.268 (2)	0.065 (4)	0.64 (8)
O2'	0.3796 (13)	0.206 (3)	0.2489 (14)	0.039 (5)	0.36 (8)
O3	0.19673 (19)	0.2307 (2)	0.24973 (15)	0.0349 (6)
O4	0.32838 (16)	0.30914 (19)	0.36998 (14)	0.0247 (5)
O5	1.33183 (18)	0.1762 (2)	0.87294 (14)	0.0283 (5)
O6	1.3101 (2)	0.3260 (3)	0.75980 (16)	0.0445 (7)
O7	1.17400 (17)	0.3012 (2)	0.84615 (16)	0.0322 (6)
N1	0.53677 (19)	0.3908 (2)	0.42520 (15)	0.0166 (5)
H1N	0.4755 (19)	0.358 (3)	0.408 (2)	0.020*
N2	1.05589 (19)	0.4233 (2)	0.70080 (15)	0.0180 (5)
H2N	1.099 (2)	0.386 (3)	0.7421 (18)	0.022*
C1	0.7249 (2)	0.4988 (3)	0.48821 (18)	0.0163 (6)
C2	0.6599 (2)	0.5394 (3)	0.41160 (18)	0.0184 (6)
H2A	0.6811	0.6052	0.3815	0.022*
C3	0.5646 (2)	0.4833 (3)	0.38005 (18)	0.0177 (6)
C4	0.5987 (2)	0.3485 (3)	0.49946 (18)	0.0164 (6)
C5	0.6942 (2)	0.4040 (3)	0.53340 (18)	0.0167 (6)
H5A	0.7379	0.3778	0.5865	0.020*
C6	0.4891 (2)	0.5170 (3)	0.29786 (19)	0.0244 (7)
H6A	0.4711	0.4472	0.2610	0.037*
H6B	0.5230	0.5759	0.2664	0.037*
H6C	0.4237	0.5499	0.3123	0.037*
C7	0.5605 (2)	0.2412 (3)	0.5387 (2)	0.0255 (7)
H7A	0.4840	0.2490	0.5389	0.038*
H7B	0.6003	0.2319	0.5988	0.038*
H7C	0.5722	0.1721	0.5042	0.038*
C8	0.8979 (2)	0.5106 (3)	0.57885 (18)	0.0164 (6)
C9	0.9320 (2)	0.5738 (3)	0.65427 (19)	0.0197 (6)
H9A	0.9006	0.6475	0.6631	0.024*
C10	1.0135 (2)	0.5270 (3)	0.71692 (19)	0.0204 (6)
C11	1.0248 (2)	0.3602 (3)	0.62686 (19)	0.0184 (6)
C12	0.9443 (2)	0.4049 (3)	0.56316 (19)	0.0178 (6)
H12A	0.9212	0.3640	0.5097	0.021*
C13	1.0564 (3)	0.5851 (3)	0.8025 (2)	0.0358 (9)
H13A	1.0534	0.5298	0.8501	0.054*
H13B	1.0131	0.6547	0.8088	0.054*
H13C	1.1308	0.6089	0.8046	0.054*
C14	1.0780 (3)	0.2449 (3)	0.6199 (2)	0.0268 (7)
H14A	1.1537	0.2503	0.6483	0.040*
H14B	1.0725	0.2247	0.5581	0.040*
H14C	1.0429	0.1839	0.6485	0.040*
C15	0.2854 (2)	0.0901 (3)	0.3686 (2)	0.0548 (13)
C16	1.3531 (3)	0.3933 (3)	0.9209 (3)	0.0378 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0170 (4)	0.0248 (4)	0.0308 (4)	−0.0001 (3)	0.0029 (3)	−0.0091 (3)
S2	0.0188 (4)	0.0357 (5)	0.0208 (4)	−0.0053 (3)	−0.0038 (3)	0.0133 (3)
F1	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F2	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F3	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F1'	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F2'	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F3'	0.0720 (13)	0.0293 (11)	0.0614 (17)	−0.0171 (9)	−0.0252 (11)	0.0380 (11)
F4	0.0295 (12)	0.0722 (17)	0.0517 (14)	−0.0213 (12)	−0.0126 (10)	0.0118 (12)
F5	0.0547 (14)	0.0371 (12)	0.0327 (11)	0.0026 (10)	−0.0012 (10)	−0.0034 (9)
F6	0.0656 (17)	0.0273 (13)	0.084 (2)	−0.0100 (12)	−0.0240 (14)	0.0171 (12)
O1	0.0126 (9)	0.0218 (11)	0.0226 (11)	−0.0023 (8)	−0.0029 (8)	0.0070 (9)
O2	0.050 (4)	0.060 (7)	0.096 (8)	0.011 (4)	0.041 (4)	−0.024 (6)
O2'	0.035 (6)	0.039 (8)	0.047 (8)	0.003 (4)	0.017 (5)	−0.011 (5)
O3	0.0352 (13)	0.0293 (13)	0.0318 (13)	−0.0027 (11)	−0.0139 (10)	−0.0049 (10)
O4	0.0194 (11)	0.0242 (12)	0.0279 (12)	−0.0032 (9)	−0.0019 (9)	−0.0056 (9)
O5	0.0270 (12)	0.0356 (13)	0.0202 (11)	0.0024 (10)	−0.0002 (9)	0.0045 (10)
O6	0.0331 (14)	0.071 (2)	0.0257 (13)	−0.0148 (13)	−0.0037 (10)	0.0244 (13)
O7	0.0202 (11)	0.0377 (14)	0.0354 (13)	−0.0016 (10)	−0.0024 (10)	0.0132 (11)
N1	0.0118 (11)	0.0201 (13)	0.0165 (12)	−0.0003 (10)	−0.0004 (9)	−0.0007 (10)
N2	0.0136 (11)	0.0239 (14)	0.0152 (12)	0.0018 (10)	−0.0004 (9)	0.0021 (10)
C1	0.0118 (13)	0.0184 (14)	0.0181 (14)	0.0011 (11)	0.0013 (11)	−0.0007 (11)
C2	0.0161 (13)	0.0225 (16)	0.0168 (14)	0.0015 (12)	0.0040 (11)	0.0058 (12)
C3	0.0162 (14)	0.0213 (15)	0.0157 (13)	0.0042 (12)	0.0035 (11)	0.0019 (12)
C4	0.0155 (13)	0.0184 (15)	0.0148 (13)	0.0021 (11)	0.0020 (11)	0.0012 (11)
C5	0.0147 (13)	0.0213 (15)	0.0130 (13)	0.0023 (11)	0.0003 (10)	0.0024 (11)
C6	0.0175 (14)	0.0340 (18)	0.0191 (15)	0.0005 (13)	−0.0026 (12)	0.0071 (13)
C7	0.0218 (15)	0.0262 (17)	0.0250 (16)	−0.0054 (13)	−0.0037 (12)	0.0070 (13)
C8	0.0104 (12)	0.0207 (15)	0.0175 (14)	−0.0027 (11)	0.0012 (10)	0.0050 (11)
C9	0.0162 (14)	0.0205 (15)	0.0228 (15)	0.0015 (12)	0.0049 (11)	−0.0001 (12)
C10	0.0172 (14)	0.0264 (16)	0.0172 (14)	−0.0002 (12)	0.0028 (11)	−0.0020 (12)
C11	0.0143 (13)	0.0212 (15)	0.0190 (14)	−0.0019 (12)	0.0012 (11)	0.0005 (12)
C12	0.0138 (13)	0.0236 (16)	0.0150 (13)	−0.0028 (12)	0.0002 (11)	−0.0018 (12)
C13	0.0367 (19)	0.042 (2)	0.0243 (17)	0.0095 (16)	−0.0037 (15)	−0.0122 (15)
C14	0.0226 (15)	0.0240 (17)	0.0303 (17)	0.0034 (13)	−0.0033 (13)	−0.0024 (14)
C15	0.040 (2)	0.025 (2)	0.080 (3)	−0.0091 (18)	−0.033 (2)	0.004 (2)
C16	0.0332 (19)	0.032 (2)	0.041 (2)	−0.0067 (16)	−0.0092 (16)	0.0111 (16)

Geometric parameters (Å, º)

S1—O2	1.422 (6)	C1—C2	1.392 (4)
S1—O3	1.435 (2)	C2—C3	1.373 (4)
S1—O4	1.448 (2)	C2—H2A	0.9500
S1—O2'	1.459 (9)	C3—C6	1.493 (4)
S1—C15	1.797 (4)	C4—C5	1.380 (4)
S2—O5	1.432 (2)	C4—C7	1.488 (4)
S2—O6	1.439 (2)	C5—H5A	0.9500
S2—O7	1.448 (2)	C6—H6A	0.9800
S2—C16	1.825 (4)	C6—H6B	0.9800
F1—C15	1.352 (4)	C6—H6C	0.9800
F2—C15	1.368 (4)	C7—H7A	0.9800
F3—C15	1.393 (4)	C7—H7B	0.9800
F1'—C15	1.364 (4)	C7—H7C	0.9800
F2'—C15	1.353 (4)	C8—C9	1.374 (4)
F3'—C15	1.314 (4)	C8—C12	1.382 (4)
F4—C16	1.335 (4)	C9—C10	1.384 (4)
F5—C16	1.334 (4)	C9—H9A	0.9500
F6—C16	1.332 (4)	C10—C13	1.493 (4)
O1—C1	1.364 (3)	C11—C12	1.376 (4)
O1—C8	1.389 (3)	C11—C14	1.489 (4)
N1—C3	1.351 (4)	C12—H12A	0.9500
N1—C4	1.354 (4)	C13—H13A	0.9800
N1—H1N	0.86 (2)	C13—H13B	0.9800
N2—C10	1.340 (4)	C13—H13C	0.9800
N2—C11	1.350 (4)	C14—H14A	0.9800
N2—H2N	0.87 (2)	C14—H14B	0.9800
C1—C5	1.386 (4)	C14—H14C	0.9800
O2—S1—O3	120.0 (12)	H7A—C7—H7C	109.5
O2—S1—O4	114.2 (5)	H7B—C7—H7C	109.5
O3—S1—O4	114.57 (14)	C9—C8—C12	122.1 (3)
O3—S1—O2'	108.6 (9)	C9—C8—O1	117.9 (3)
O4—S1—O2'	112.7 (8)	C12—C8—O1	119.9 (3)
O2—S1—C15	98.1 (16)	C8—C9—C10	118.1 (3)
O3—S1—C15	102.94 (14)	C8—C9—H9A	121.0
O4—S1—C15	102.87 (14)	C10—C9—H9A	121.0
O2'—S1—C15	114.8 (13)	N2—C10—C9	118.6 (3)
O5—S2—O6	115.54 (17)	N2—C10—C13	117.8 (3)
O5—S2—O7	115.02 (14)	C9—C10—C13	123.6 (3)
O6—S2—O7	113.47 (15)	N2—C11—C12	118.2 (3)
O5—S2—C16	103.86 (15)	N2—C11—C14	118.0 (3)
O6—S2—C16	103.92 (17)	C12—C11—C14	123.8 (3)
O7—S2—C16	102.88 (17)	C11—C12—C8	118.4 (3)
C1—O1—C8	119.3 (2)	C11—C12—H12A	120.8
C3—N1—C4	123.6 (2)	C8—C12—H12A	120.8
C3—N1—H1N	119 (2)	C10—C13—H13A	109.5
C4—N1—H1N	117 (2)	C10—C13—H13B	109.5
C10—N2—C11	124.5 (3)	H13A—C13—H13B	109.5
C10—N2—H2N	120 (2)	C10—C13—H13C	109.5
C11—N2—H2N	114 (2)	H13A—C13—H13C	109.5
O1—C1—C5	123.4 (2)	H13B—C13—H13C	109.5
O1—C1—C2	115.6 (3)	C11—C14—H14A	109.5
C5—C1—C2	121.0 (3)	C11—C14—H14B	109.5
C3—C2—C1	119.2 (3)	H14A—C14—H14B	109.5
C3—C2—H2A	120.4	C11—C14—H14C	109.5
C1—C2—H2A	120.4	H14A—C14—H14C	109.5
N1—C3—C2	118.6 (3)	H14B—C14—H14C	109.5
N1—C3—C6	117.2 (3)	F3'—C15—F2'	112.1 (4)
C2—C3—C6	124.2 (3)	F3'—C15—F1'	113.4 (4)
N1—C4—C5	119.1 (3)	F2'—C15—F1'	104.6 (4)
N1—C4—C7	117.4 (3)	F1—C15—F2	103.8 (4)
C5—C4—C7	123.4 (3)	F1—C15—F3	101.0 (4)
C4—C5—C1	118.4 (3)	F2—C15—F3	102.9 (4)
C4—C5—H5A	120.8	F3'—C15—S1	120.6 (3)
C1—C5—H5A	120.8	F1—C15—S1	122.0 (3)
C3—C6—H6A	109.5	F2'—C15—S1	102.7 (3)
C3—C6—H6B	109.5	F1'—C15—S1	101.5 (3)
H6A—C6—H6B	109.5	F2—C15—S1	121.0 (3)
C3—C6—H6C	109.5	F3—C15—S1	102.5 (3)
H6A—C6—H6C	109.5	F6—C16—F5	107.7 (3)
H6B—C6—H6C	109.5	F6—C16—F4	107.9 (3)
C4—C7—H7A	109.5	F5—C16—F4	107.7 (3)
C4—C7—H7B	109.5	F6—C16—S2	111.2 (2)
H7A—C7—H7B	109.5	F5—C16—S2	111.3 (2)
C4—C7—H7C	109.5	F4—C16—S2	110.9 (3)
C8—O1—C1—C5	15.1 (4)	O2'—S1—C15—F3'	−178.5 (8)
C8—O1—C1—C2	−165.8 (3)	O2—S1—C15—F1	−63.4 (9)
O1—C1—C2—C3	−180.0 (3)	O3—S1—C15—F1	60.0 (4)
C5—C1—C2—C3	−0.9 (4)	O4—S1—C15—F1	179.4 (4)
C4—N1—C3—C2	−1.3 (4)	O2'—S1—C15—F1	−57.7 (9)
C4—N1—C3—C6	178.2 (3)	O2—S1—C15—F2'	50.2 (9)
C1—C2—C3—N1	0.6 (4)	O3—S1—C15—F2'	173.7 (4)
C1—C2—C3—C6	−178.8 (3)	O4—S1—C15—F2'	−67.0 (4)
C3—N1—C4—C5	2.1 (4)	O2'—S1—C15—F2'	55.9 (9)
C3—N1—C4—C7	−176.1 (3)	O2—S1—C15—F1'	−57.8 (8)
N1—C4—C5—C1	−2.2 (4)	O3—S1—C15—F1'	65.6 (3)
C7—C4—C5—C1	175.8 (3)	O4—S1—C15—F1'	−175.0 (3)
O1—C1—C5—C4	−179.3 (3)	O2'—S1—C15—F1'	−52.2 (8)
C2—C1—C5—C4	1.6 (4)	O2—S1—C15—F2	71.3 (9)
C1—O1—C8—C9	−121.9 (3)	O3—S1—C15—F2	−165.3 (4)
C1—O1—C8—C12	61.5 (3)	O4—S1—C15—F2	−45.9 (4)
C12—C8—C9—C10	−1.9 (4)	O2'—S1—C15—F2	76.9 (9)
O1—C8—C9—C10	−178.4 (2)	O2—S1—C15—F3	−175.1 (8)
C11—N2—C10—C9	0.1 (4)	O3—S1—C15—F3	−51.7 (3)
C11—N2—C10—C13	179.5 (3)	O4—S1—C15—F3	67.7 (3)
C8—C9—C10—N2	0.7 (4)	O2'—S1—C15—F3	−169.4 (8)
C8—C9—C10—C13	−178.6 (3)	O5—S2—C16—F6	−178.0 (3)
C10—N2—C11—C12	0.3 (4)	O6—S2—C16—F6	60.8 (3)
C10—N2—C11—C14	−178.4 (3)	O7—S2—C16—F6	−57.8 (3)
N2—C11—C12—C8	−1.4 (4)	O5—S2—C16—F5	−57.9 (3)
C14—C11—C12—C8	177.2 (3)	O6—S2—C16—F5	−179.2 (3)
C9—C8—C12—C11	2.3 (4)	O7—S2—C16—F5	62.3 (3)
O1—C8—C12—C11	178.7 (2)	O5—S2—C16—F4	62.0 (3)
O2—S1—C15—F3'	175.9 (9)	O6—S2—C16—F4	−59.3 (3)
O3—S1—C15—F3'	−60.7 (4)	O7—S2—C16—F4	−177.8 (2)
O4—S1—C15—F3'	58.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.86 (2)	1.93 (2)	2.783 (3)	171 (3)
N2—H2N···O7	0.87 (2)	1.97 (2)	2.826 (3)	169 (3)
C2—H2A···O6^i	0.95	2.36	3.170 (4)	142
C6—H6B···O6^i	0.98	2.50	3.383 (4)	149
C7—H7B···O3^ii	0.98	2.47	3.421 (4)	164
C9—H9A···O3^iii	0.95	2.44	3.293 (4)	149
C12—H12A···O5^iv	0.95	2.26	3.168 (4)	160
C14—H14A···O6	0.98	2.52	3.436 (4)	155

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