9-(2-Ethyl­phenoxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

In the crystal structure of the title compound, C₂₃H₂₀NO₂⁺·CF₃SO₃⁻, the cations form inversion dimers through π–π inter­actions between the acridine ring systems. These dimers are further linked by C—H...π inter­actions. The cations and anions are connected by C—H...O and C—F...π inter­actions. The acridine and benzene ring systems are oriented at a dihedral angle of 20.8 (1)°. The carboxyl group is twisted at an angle of 66.2 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel in the lattice.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.116
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H5     ..  H26A    ..       1.85 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         40 Ang.
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         S27
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C31

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C24 H20 F3 N1 O5 S1
            Atom count from _chemical_formula_moiety:C24 H20 F3 N1 O5
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        300 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

9-(Phenoxycarbonyl)-10-alkylacridinium salts have long been known as chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels (Zomer & Jacquemijns, 2001). These compounds are commonly applied in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Roda et al., 2003; Brown et al., 2009). The reaction of the cations of these salts with hydrogen peroxide in alkaline media produces light. Our own investigations (Rak et al., 1999) and those of others (Zomer et al., 2001) have revealed that oxidation of acridinium chemiluminogens is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining molecules to electronically excited, light-emitting 10-alkyl-9-acridinones. It has been found that the efficiency of chemiluminescence – crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). In the search for efficient chemiluminogens we undertook investigations on 9-(phenoxycarbonyl)-10-methylacridinium derivatives substituted in the phenyl fragment. Here we present the structure of one such derivative.

In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium moiety are typical of acridine-based derivatives (Sikorski et al., 2005a,b). With respective average deviations from planarity of 0.022 (3) Å and 0.002 (3) Å, the acridine and benzene ring systems are oriented at 20.8 (1)°. The carboxyl group is twisted at an angle of 66.2 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle of 0.0 (1)°) in the lattice. The mutual arrangement of the carboxyl group relative to the acridine skeleton is similar in the compound investigated and its precursor – 2-ethylphenyl acridine-9-carboxylate (Sikorski et al., 2005a). On the other hand, the acridine and benzene ring systems are oriented quite differently in the compound investigated and its precursor.

In the crystal structure, the inversely oriented cations form dimers through multidirectional π–π interactions involving acridine moieties (Table 3, Fig. 2). These dimers are linked by C–H···O (Table 1, Fig. 2) and C–F···π (Table 2, Fig. 2) interactions to adjacent anions, and by C–H···π (Table 1, Fig. 2) interactions to neighboring cations. The C–H···O interactions are of the hydrogen bond type (Steiner, 1999; Bianchi et al. 2004). The C–H···π interactions should be of an attractive nature (Takahashi et al., 2001), like the C–F···π (Dorn et al., 2005) and the π–π (Hunter et al., 2001) interactions. The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

Related literature

For general background to 9-(phenoxycarbonyl)-10-alkylacridinium salts, see: Brown et al. (2009); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2005a,b). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Steiner (1999); Takahashi et al. (2001). For the synthesis, see: Niziołek et al. (2008); Sato (1996).

S2. Experimental

The compound was synthesized in three steps (Niziołek et al., 2008). First, 9-(chlorocarbonyl)-acridine was produced by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride. Then, esterification with 2-ethylphenol was carried out in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15h) (Sato, 1996). The crude product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 3/2 v/v). The 2-ethylphenyl acridine-9-carboxylate thus obtained was quaternarized with a five-fold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane. The crude 9-(2-ethylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 25 v/v excess of diethyl ether. Yellow crystals suitable suitable for X-Ray investigations were grown from absolute ethanol solution (m.p. 470-471 K).

S3. Refinement

H atoms were positioned geometrically, with C—H = 0.93 Å and 0.96 Å for the aromatic and alkyl H atoms, respectively, and constrained to ride on their parrent atoms with U_iso(H) = xU_eq(C), where x = 1.2 for the aromatic and x = 1.5 for the alkyl H atoms.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radius. Cg1, Cg2, Cg3 and Cg4 denote the ring centroids.
	Fig. 2. The arrangement of the ions in the crystal structure. The C–H···O interactions are represented by dashed lines, the C–H···π, C–F···π and π–π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) x + 1, y, z + 1; (ii) x + 1, y, z; (iii) –x + 1, –y + 2, –z + 2; (iv) –x + 1, –y + 2, –z + 1; (v) –x + 1, –y + 1, –z + 1.]

9-(2-Ethylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

Crystal data

C23H20NO2^+·CF3O3S^−	Z = 2
Mr = 491.47	F(000) = 508
Triclinic, P1	Dx = 1.484 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8519 (4) Å	Cell parameters from 10425 reflections
b = 10.9533 (4) Å	θ = 3.1–29.2°
c = 11.7805 (4) Å	µ = 0.21 mm^−1
α = 104.379 (3)°	T = 295 K
β = 101.475 (3)°	Block, yellow
γ = 109.983 (3)°	0.40 × 0.35 × 0.20 mm
V = 1099.61 (7) Å^3

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	2956 reflections with I > 2σ(I)
Radiation source: Enhanced (Mo) X-ray Source	Rint = 0.039
Graphite monochromator	θmax = 25.1°, θmin = 3.1°
Detector resolution: 10.4002 pixels mm^-1	h = −11→11
ω scans	k = −13→13
21109 measured reflections	l = −14→14
3914 independent reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0737P)^2] where P = (Fo^2 + 2Fc^2)/3
3914 reflections	(Δ/σ)max < 0.001
309 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
C8	0.4629 (2)	0.70220 (17)	0.44477 (16)	0.0468 (4)
H8	0.3781	0.7136	0.4600	0.056*
C7	0.4857 (2)	0.69994 (19)	0.33477 (18)	0.0561 (5)
H7	0.4164	0.7087	0.2745	0.067*
C6	0.6146 (3)	0.68432 (19)	0.31214 (18)	0.0573 (5)
H6	0.6298	0.6842	0.2367	0.069*
C5	0.7175 (2)	0.66940 (17)	0.39617 (17)	0.0508 (5)
H5	0.8014	0.6591	0.3780	0.061*
C4	0.8753 (2)	0.62222 (19)	0.79550 (18)	0.0535 (5)
H4	0.9549	0.6038	0.7759	0.064*
C3	0.8550 (2)	0.6234 (2)	0.90569 (19)	0.0583 (5)
H3	0.9214	0.6064	0.9612	0.070*
C2	0.7358 (2)	0.64984 (19)	0.93822 (18)	0.0559 (5)
H2	0.7247	0.6518	1.0151	0.067*
C1	0.6372 (2)	0.67241 (18)	0.85755 (16)	0.0499 (5)
H1	0.5573	0.6881	0.8792	0.060*
C9	0.55076 (18)	0.69321 (15)	0.65368 (15)	0.0374 (4)
N10	0.79811 (15)	0.65304 (13)	0.59893 (13)	0.0419 (3)
C13	0.56732 (19)	0.68738 (15)	0.53759 (15)	0.0381 (4)
C14	0.69716 (19)	0.66950 (15)	0.51165 (15)	0.0403 (4)
C11	0.65277 (19)	0.67276 (16)	0.74035 (15)	0.0394 (4)
C12	0.77656 (19)	0.64875 (15)	0.70957 (15)	0.0404 (4)
C15	0.4184 (2)	0.71774 (16)	0.68401 (15)	0.0389 (4)
O16	0.46656 (13)	0.83893 (11)	0.77566 (10)	0.0435 (3)
O17	0.28868 (14)	0.63985 (12)	0.63199 (12)	0.0554 (4)
C18	0.3528 (2)	0.88341 (16)	0.80457 (16)	0.0439 (4)
C19	0.3118 (2)	0.86926 (16)	0.90748 (17)	0.0478 (4)
C20	0.2093 (2)	0.92574 (19)	0.9350 (2)	0.0615 (6)
H20	0.1775	0.9189	1.0032	0.074*
C21	0.1550 (3)	0.9905 (2)	0.8641 (2)	0.0690 (6)
H21	0.0875	1.0273	0.8851	0.083*
C22	0.1986 (3)	1.0024 (2)	0.7621 (2)	0.0671 (6)
H22	0.1602	1.0460	0.7140	0.080*
C23	0.3001 (2)	0.94881 (18)	0.73174 (19)	0.0552 (5)
H23	0.3321	0.9567	0.6637	0.066*
C24	0.3714 (2)	0.79938 (18)	0.98693 (17)	0.0554 (5)
H24A	0.3664	0.8357	1.0692	0.067*
H24B	0.4774	0.8221	0.9933	0.067*
C25	0.2850 (3)	0.6427 (2)	0.9388 (2)	0.0644 (5)
H25A	0.3346	0.6040	0.9891	0.097*
H25B	0.2832	0.6063	0.8552	0.097*
H25C	0.1828	0.6189	0.9416	0.097*
C26	0.9362 (2)	0.6389 (2)	0.5764 (2)	0.0623 (5)
H26A	0.9481	0.6594	0.5034	0.093*
H26B	0.9257	0.5459	0.5655	0.093*
H26C	1.0239	0.7022	0.6456	0.093*
S27	0.07676 (5)	0.73990 (4)	0.26699 (4)	0.04742 (17)
O28	−0.07260 (15)	0.73377 (15)	0.22221 (13)	0.0649 (4)
O29	0.09669 (19)	0.68219 (15)	0.36225 (14)	0.0740 (4)
O30	0.14440 (18)	0.70502 (16)	0.17469 (13)	0.0743 (4)
C31	0.1906 (3)	0.9229 (2)	0.3455 (2)	0.0740 (6)
F32	0.1421 (2)	0.97409 (17)	0.43606 (15)	0.1282 (7)
F33	0.1861 (2)	0.99425 (14)	0.27126 (17)	0.1192 (6)
F34	0.33510 (19)	0.95023 (16)	0.39672 (18)	0.1263 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C8	0.0487 (11)	0.0493 (10)	0.0471 (10)	0.0242 (9)	0.0164 (9)	0.0174 (8)
C7	0.0650 (14)	0.0608 (11)	0.0476 (11)	0.0298 (10)	0.0164 (10)	0.0226 (9)
C6	0.0724 (14)	0.0590 (11)	0.0465 (11)	0.0259 (10)	0.0281 (10)	0.0219 (9)
C5	0.0521 (12)	0.0501 (10)	0.0548 (11)	0.0202 (9)	0.0292 (10)	0.0168 (8)
C4	0.0414 (11)	0.0578 (11)	0.0627 (12)	0.0277 (9)	0.0110 (9)	0.0169 (9)
C3	0.0565 (13)	0.0641 (12)	0.0565 (12)	0.0317 (10)	0.0074 (10)	0.0226 (9)
C2	0.0645 (13)	0.0650 (12)	0.0485 (11)	0.0358 (11)	0.0167 (10)	0.0240 (9)
C1	0.0541 (12)	0.0592 (11)	0.0501 (10)	0.0328 (9)	0.0219 (9)	0.0233 (9)
C9	0.0346 (9)	0.0342 (8)	0.0447 (9)	0.0151 (7)	0.0147 (7)	0.0123 (7)
N10	0.0325 (8)	0.0425 (7)	0.0491 (8)	0.0162 (6)	0.0158 (7)	0.0096 (6)
C13	0.0388 (9)	0.0344 (8)	0.0409 (9)	0.0157 (7)	0.0134 (7)	0.0109 (7)
C14	0.0402 (10)	0.0351 (8)	0.0429 (9)	0.0134 (7)	0.0168 (8)	0.0090 (7)
C11	0.0379 (10)	0.0372 (8)	0.0438 (9)	0.0171 (7)	0.0133 (8)	0.0125 (7)
C12	0.0354 (9)	0.0366 (8)	0.0447 (10)	0.0145 (7)	0.0107 (8)	0.0086 (7)
C15	0.0401 (11)	0.0419 (9)	0.0410 (9)	0.0212 (8)	0.0151 (8)	0.0166 (7)
O16	0.0375 (7)	0.0442 (6)	0.0504 (7)	0.0205 (5)	0.0174 (6)	0.0106 (5)
O17	0.0375 (8)	0.0531 (7)	0.0640 (8)	0.0168 (6)	0.0143 (6)	0.0053 (6)
C18	0.0367 (10)	0.0373 (8)	0.0559 (11)	0.0181 (7)	0.0156 (8)	0.0079 (8)
C19	0.0435 (10)	0.0404 (9)	0.0545 (11)	0.0151 (8)	0.0194 (9)	0.0082 (8)
C20	0.0549 (13)	0.0570 (11)	0.0730 (13)	0.0250 (10)	0.0312 (11)	0.0116 (10)
C21	0.0579 (14)	0.0588 (12)	0.0956 (17)	0.0356 (11)	0.0316 (13)	0.0131 (12)
C22	0.0613 (14)	0.0552 (11)	0.0932 (16)	0.0354 (11)	0.0211 (12)	0.0257 (11)
C23	0.0530 (12)	0.0502 (10)	0.0668 (12)	0.0251 (9)	0.0205 (10)	0.0203 (9)
C24	0.0553 (12)	0.0599 (11)	0.0536 (11)	0.0243 (10)	0.0252 (10)	0.0163 (9)
C25	0.0621 (14)	0.0642 (12)	0.0767 (14)	0.0260 (10)	0.0307 (11)	0.0335 (11)
C26	0.0382 (11)	0.0780 (13)	0.0666 (13)	0.0265 (10)	0.0203 (10)	0.0117 (11)
S27	0.0507 (3)	0.0533 (3)	0.0460 (3)	0.0255 (2)	0.0210 (2)	0.0191 (2)
O28	0.0476 (9)	0.0797 (9)	0.0687 (9)	0.0282 (7)	0.0186 (7)	0.0245 (7)
O29	0.0943 (12)	0.0861 (10)	0.0733 (10)	0.0504 (9)	0.0386 (9)	0.0506 (8)
O30	0.0806 (11)	0.1006 (11)	0.0617 (9)	0.0510 (9)	0.0407 (8)	0.0266 (8)
C31	0.0712 (17)	0.0610 (13)	0.0783 (15)	0.0277 (12)	0.0042 (13)	0.0196 (12)
F32	0.1628 (18)	0.1019 (12)	0.0962 (11)	0.0735 (12)	0.0201 (12)	−0.0158 (9)
F33	0.1130 (13)	0.0720 (9)	0.1535 (15)	0.0184 (9)	0.0082 (11)	0.0619 (10)
F34	0.0701 (11)	0.0882 (10)	0.1607 (16)	0.0141 (9)	−0.0251 (11)	0.0193 (10)

Geometric parameters (Å, º)

C8—C7	1.354 (3)	O16—C18	1.432 (2)
C8—C13	1.427 (2)	C18—C23	1.379 (2)
C8—H8	0.9300	C18—C19	1.380 (3)
C7—C6	1.405 (3)	C19—C20	1.401 (3)
C7—H7	0.9300	C19—C24	1.500 (3)
C6—C5	1.352 (3)	C20—C21	1.365 (3)
C6—H6	0.9300	C20—H20	0.9300
C5—C14	1.414 (2)	C21—C22	1.375 (3)
C5—H5	0.9300	C21—H21	0.9300
C4—C3	1.350 (3)	C22—C23	1.382 (3)
C4—C12	1.416 (3)	C22—H22	0.9300
C4—H4	0.9300	C23—H23	0.9300
C3—C2	1.402 (3)	C24—C25	1.523 (3)
C3—H3	0.9300	C24—H24A	0.9700
C2—C1	1.349 (3)	C24—H24B	0.9700
C2—H2	0.9300	C25—H25A	0.9600
C1—C11	1.420 (2)	C25—H25B	0.9600
C1—H1	0.9300	C25—H25C	0.9600
C9—C13	1.398 (2)	C26—H26A	0.9600
C9—C11	1.401 (2)	C26—H26B	0.9600
C9—C15	1.509 (2)	C26—H26C	0.9600
N10—C12	1.371 (2)	S27—O30	1.4242 (14)
N10—C14	1.374 (2)	S27—O29	1.4307 (14)
N10—C26	1.488 (2)	S27—O28	1.4331 (15)
C13—C14	1.437 (2)	S27—C31	1.806 (2)
C11—C12	1.427 (2)	C31—F33	1.314 (3)
C15—O17	1.192 (2)	C31—F34	1.326 (3)
C15—O16	1.3442 (19)	C31—F32	1.330 (3)
C7—C8—C13	120.82 (17)	C23—C18—O16	116.69 (16)
C7—C8—H8	119.6	C19—C18—O16	119.15 (16)
C13—C8—H8	119.6	C18—C19—C20	115.51 (18)
C8—C7—C6	119.67 (19)	C18—C19—C24	123.48 (16)
C8—C7—H7	120.2	C20—C19—C24	121.01 (18)
C6—C7—H7	120.2	C21—C20—C19	121.7 (2)
C5—C6—C7	122.33 (18)	C21—C20—H20	119.1
C5—C6—H6	118.8	C19—C20—H20	119.1
C7—C6—H6	118.8	C20—C21—C22	120.97 (19)
C6—C5—C14	119.89 (18)	C20—C21—H21	119.5
C6—C5—H5	120.1	C22—C21—H21	119.5
C14—C5—H5	120.1	C21—C22—C23	119.4 (2)
C3—C4—C12	120.51 (18)	C21—C22—H22	120.3
C3—C4—H4	119.7	C23—C22—H22	120.3
C12—C4—H4	119.7	C18—C23—C22	118.5 (2)
C4—C3—C2	121.39 (18)	C18—C23—H23	120.8
C4—C3—H3	119.3	C22—C23—H23	120.8
C2—C3—H3	119.3	C19—C24—C25	113.77 (17)
C1—C2—C3	119.77 (19)	C19—C24—H24A	108.8
C1—C2—H2	120.1	C25—C24—H24A	108.8
C3—C2—H2	120.1	C19—C24—H24B	108.8
C2—C1—C11	121.50 (18)	C25—C24—H24B	108.8
C2—C1—H1	119.2	H24A—C24—H24B	107.7
C11—C1—H1	119.2	C24—C25—H25A	109.5
C13—C9—C11	120.83 (15)	C24—C25—H25B	109.5
C13—C9—C15	119.28 (15)	H25A—C25—H25B	109.5
C11—C9—C15	119.87 (15)	C24—C25—H25C	109.5
C12—N10—C14	121.94 (14)	H25A—C25—H25C	109.5
C12—N10—C26	117.26 (16)	H25B—C25—H25C	109.5
C14—N10—C26	120.80 (15)	N10—C26—H26A	109.5
C9—C13—C8	122.77 (15)	N10—C26—H26B	109.5
C9—C13—C14	118.70 (16)	H26A—C26—H26B	109.5
C8—C13—C14	118.51 (15)	N10—C26—H26C	109.5
N10—C14—C5	121.66 (16)	H26A—C26—H26C	109.5
N10—C14—C13	119.56 (15)	H26B—C26—H26C	109.5
C5—C14—C13	118.77 (17)	O30—S27—O29	114.62 (9)
C9—C11—C1	122.87 (16)	O30—S27—O28	115.38 (9)
C9—C11—C12	119.01 (15)	O29—S27—O28	115.01 (9)
C1—C11—C12	118.12 (16)	O30—S27—C31	103.15 (11)
N10—C12—C4	121.62 (16)	O29—S27—C31	103.45 (10)
N10—C12—C11	119.71 (15)	O28—S27—C31	102.78 (10)
C4—C12—C11	118.67 (16)	F33—C31—F34	107.8 (2)
O17—C15—O16	125.00 (15)	F33—C31—F32	106.5 (2)
O17—C15—C9	123.94 (15)	F34—C31—F32	106.5 (2)
O16—C15—C9	111.05 (14)	F33—C31—S27	112.23 (16)
C15—O16—C18	117.14 (13)	F34—C31—S27	112.05 (16)
C23—C18—C19	123.94 (16)	F32—C31—S27	111.42 (18)
C13—C8—C7—C6	−0.7 (3)	C9—C11—C12—N10	3.3 (2)
C8—C7—C6—C5	0.9 (3)	C1—C11—C12—N10	−177.78 (14)
C7—C6—C5—C14	−0.1 (3)	C9—C11—C12—C4	−177.29 (15)
C12—C4—C3—C2	0.4 (3)	C1—C11—C12—C4	1.6 (2)
C4—C3—C2—C1	1.1 (3)	C13—C9—C15—O17	63.9 (2)
C3—C2—C1—C11	−1.2 (3)	C11—C9—C15—O17	−114.36 (19)
C11—C9—C13—C8	177.50 (15)	C13—C9—C15—O16	−115.39 (16)
C15—C9—C13—C8	−0.7 (2)	C11—C9—C15—O16	66.40 (18)
C11—C9—C13—C14	−4.3 (2)	O17—C15—O16—C18	−6.3 (2)
C15—C9—C13—C14	177.54 (13)	C9—C15—O16—C18	172.96 (13)
C7—C8—C13—C9	178.04 (16)	C15—O16—C18—C23	−82.25 (18)
C7—C8—C13—C14	−0.2 (2)	C15—O16—C18—C19	102.93 (18)
C12—N10—C14—C5	−177.94 (14)	C23—C18—C19—C20	0.5 (3)
C26—N10—C14—C5	2.0 (2)	O16—C18—C19—C20	174.87 (14)
C12—N10—C14—C13	2.1 (2)	C23—C18—C19—C24	−179.24 (17)
C26—N10—C14—C13	−178.01 (14)	O16—C18—C19—C24	−4.8 (2)
C6—C5—C14—N10	179.25 (16)	C18—C19—C20—C21	−0.2 (3)
C6—C5—C14—C13	−0.8 (2)	C24—C19—C20—C21	179.50 (18)
C9—C13—C14—N10	2.6 (2)	C19—C20—C21—C22	0.3 (3)
C8—C13—C14—N10	−179.08 (14)	C20—C21—C22—C23	−0.6 (3)
C9—C13—C14—C5	−177.38 (14)	C19—C18—C23—C22	−0.8 (3)
C8—C13—C14—C5	0.9 (2)	O16—C18—C23—C22	−175.31 (16)
C13—C9—C11—C1	−177.50 (15)	C21—C22—C23—C18	0.8 (3)
C15—C9—C11—C1	0.7 (2)	C18—C19—C24—C25	−83.8 (2)
C13—C9—C11—C12	1.4 (2)	C20—C19—C24—C25	96.5 (2)
C15—C9—C11—C12	179.56 (13)	O30—S27—C31—F33	60.3 (2)
C2—C1—C11—C9	178.74 (17)	O29—S27—C31—F33	−179.97 (18)
C2—C1—C11—C12	−0.1 (3)	O28—S27—C31—F33	−60.0 (2)
C14—N10—C12—C4	175.56 (15)	O30—S27—C31—F34	−61.1 (2)
C26—N10—C12—C4	−4.4 (2)	O29—S27—C31—F34	58.6 (2)
C14—N10—C12—C11	−5.0 (2)	O28—S27—C31—F34	178.62 (18)
C26—N10—C12—C11	175.04 (14)	O30—S27—C31—F32	179.70 (16)
C3—C4—C12—N10	177.62 (16)	O29—S27—C31—F32	−60.58 (18)
C3—C4—C12—C11	−1.8 (3)	O28—S27—C31—F32	59.41 (18)

Hydrogen-bond geometry (Å, º)

Cg4 is the centroid of the C18–C23 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O28^i	0.93	2.55	3.221 (2)	130
C5—H5···O28^ii	0.93	2.56	3.222 (3)	129
C24—H24B···Cg4^iii	0.96	2.92	3.603 (2)	129
C26—H26A···O29^ii	0.96	2.43	3.280 (3)	148
C26—H26C···Cg4^ii	0.96	2.80	3.741 (2)	165

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