S-Di­ethyl­amino-S-(3-methyl­benzoyl­imino)-S,S-di­phenyl­sulfonium tetra­fluoro­borate

Sheikh, M.C.; Yoshimura, T.; Miyatake, R.; Hanawa, S.

doi:10.1107/S241431461901040X

organic compounds

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ISSN: 2414-3146

Volume 4| Part 7| July 2019| x191040

https://doi.org/10.1107/S241431461901040X

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S-Diethylamino-S-(3-methylbenzoylimino)-S,S-diphenylsulfonium tetrafluoroborate

Md Chanmiya Sheikh,^a Toshiaki Yoshimura,^a ^* Ryuta Miyatake ^b and Soichiro Hanawa ^a

^aDepartment of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan, and ^bCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan
^*Correspondence e-mail: by4ut6@bma.biglobe.ne.jp

Edited by H. Ishida, Okayama University, Japan (Received 9 July 2019; accepted 22 July 2019; online 30 July 2019)

The title salt, C₂₄H₂₇N₂OS⁺·BF₄⁻, was prepared by an alkylation at the amino N atom attached to the sulfur atom of the corresponding sulfodiimide. The configuration around the sulfur atom is a slightly distorted tetrahedral geometry with two S—N bonds and two S—C bonds. The lengths of the S—N(diethylamine) and S=N(m-methylbenzoylimine) bonds are 1.619 (2) and 1.551 (2) Å, respectively. The two N—S—N—C(ethyl) and the N—S—N—C(m-methylbenzoylimine) torsion angles are −85.43 (3), 58.94 (17) and 62.03 (16)°, respectively. The dihedral angle between the two phenyl rings is 84.03 (14)°. In the crystal, C—H⋯F hydrogen bonds link the cation and anion, forming a three-dimensional network.

Keywords: crystal structure; N-ethyl-N-(3-methylbenzoyl)-S,S-diphenylsulfodiimide; meerwein reagent; iminosulfonium salt; hydrogen bonding.

CCDC reference: 1449252

Structure description

The chemistry of sulfur(VI) sulfonium compounds such as oxosulfonium salts is very interesting because of their anomalous reactivity (Mori et al., 1990 ; Kennewell & Taylor, 1975 ). However, only a few iminosulfonium salts, which are isoelectronic with the oxosulfonium salts, have been reported (Glemser & Mews, 1980 ; Labbow et al., 2016 ). In view of the anomalous reactivity of these salts, we report herein on the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is illustrated in Fig. 1. The S1=N1 (m-methylbenzoylimine) and S1—N2 (diethylamine) bond lengths are 1.551 (2) and 1.619 (2) Å, respectively. These bonds are significantly longer than the S≡N triple bond of triphenylsulfanenitrile (1.462 Å; Yoshimura et al., 1997 ), and close to the S=N double bonds of S,S-dimethylsulfonediimine (1.533 Å, electron diffraction study; Oberhammer et al., 1970 ), S,S-diphenyl-S-pyrrolidinoiminosulfonium perchlorate [1.503 (2) Å for S—N (NH), X-ray; Sheikh et al., 2017 ], sulfonediiminosulfonium salt [1.599 (3) Å for S—N; Ohkubo et al., 1997 ], S,S-diphenyl-S-tosyl sulfone diimine [1.515 (18) Å for S—N (NH) and 1.5785 (15) Å for S—N (p-toluenesulfonyl), X-ray; Sheikh et al., 2019b ] and N-ethyl-N-(3-methylbenzoyl)-S,S-diphenylsulfodiimide [1.528 (2) Å for S—N (NEt) and 1.584 (3) Å for S—N (m-methylbenzoyl), X-ray; Sheikh et al., 2019a ], and shorter than that of S,S-diphenyl-N-tosylsulfilimine (1.628 Å, X-ray; Kálmán et al., 1971 ). In the crystal, the cation and the anion are linked through weak C—H⋯F hydrogen bonds (Table 1), forming a three-dimensional network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H6⋯F3ⁱ	0.98	2.50	3.446 (4)	163
C10—H8⋯F4	0.95	2.48	3.202 (5)	133
C14—H12⋯F3ⁱⁱ	0.95	2.51	3.433 (3)	165
C16—H13⋯F2ⁱⁱ	0.95	2.61	3.367 (4)	137
C16—H13⋯F3ⁱⁱ	0.95	2.55	3.450 (4)	158
C18—H15⋯F1ⁱⁱⁱ	0.95	2.33	3.200 (5)	150
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
A packing view of the title compound, showing C—H⋯F hydrogen bonds (blue dashed lines).

Synthesis and crystallization

The compound precursor, N-ethyl-N-(3-methylbenzoyl)-S,S-diphenylsulfodiimide (363 mg, 1.0 mmol) was allowed to react with triethyloxonium tetrafluoroborate (209 mg, 1.1 mmol) in dry CH₂Cl₂ (30 ml) under argon atmosphere at a temperature of 0°C for 4 h. The reaction mixture was poured into water, and extracted with CHCl₃ (3 × 15 ml). The combined organic extracts were washed with water, dried over anhydrous MgSO₄. The solution was concentrated under reduced pressure afforded the desired product (yield: 316 mg, 66%) as a colourless solid. Single crystals were obtained from an acetone/ether (2:1 v/v) solution (m.p. 169.5–170.5°C).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₂₇N₂OS⁺·BF₄⁻
M_r	478.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.9291 (3), 12.6437 (3), 16.3467 (3)
β (°)	103.5043 (7)
V (Å³)	2397.36 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.64
Crystal size (mm)	0.67 × 0.54 × 0.52

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.256, 0.426
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	26225, 4382, 3856
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.168, 1.05
No. of reflections	4382
No. of parameters	301
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.48
Computer programs: RAPID-AUTO (Rigaku, 2001 ), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ) and CrystalStructure (Rigaku, 2010 ).

Structural data

CCDC reference: 1449252

Crystal structure: contains datablocks General, I. DOI: https://doi.org/10.1107/S241431461901040X/is4035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461901040X/is4035Isup2.hkl

checkCIF report

Computing details top

Cell refinement: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

S-Diethylamino-S-(3-methylbenzoylimino)-S,S-diphenylsulfonium tetrafluoroborate top

Crystal data top

C₂₄H₂₇N₂OS⁺·BF₄⁻	F(000) = 1000.00
M_r = 478.35	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 22845 reflections
a = 11.9291 (3) Å	θ = 3.5–68.3°
b = 12.6437 (3) Å	µ = 1.64 mm⁻¹
c = 16.3467 (3) Å	T = 173 K
β = 103.5043 (7)°	Prism, colorless
V = 2397.36 (8) Å³	0.67 × 0.54 × 0.52 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3856 reflections with F² > 2.0σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.082
ω scans	θ_max = 68.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
T_min = 0.256, T_max = 0.426	k = −15→15
26225 measured reflections	l = −19→19
4382 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0927P)² + 1.2365P] where P = (F_o² + 2F_c²)/3
4382 reflections	(Δ/σ)_max = 0.001
301 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.75784 (4)	0.11353 (4)	0.51723 (3)	0.03166 (19)
F1	0.7005 (3)	−0.0580 (3)	0.8507 (3)	0.1658 (15)
F2	0.6448 (3)	0.1055 (3)	0.80659 (19)	0.1504 (14)
F3	0.8184 (3)	0.0744 (2)	0.88636 (13)	0.1083 (8)
F4	0.7734 (3)	0.0159 (3)	0.75575 (14)	0.1263 (10)
O1	0.86944 (15)	−0.07847 (13)	0.50778 (12)	0.0504 (5)
N1	0.72177 (16)	0.00692 (14)	0.55045 (11)	0.0375 (5)
N2	0.75769 (16)	0.13263 (15)	0.41929 (11)	0.0365 (5)
C1	0.75160 (19)	−0.18041 (17)	0.57664 (13)	0.0371 (5)
C2	0.8086 (2)	−0.27349 (18)	0.56551 (14)	0.0417 (6)
C3	0.7792 (3)	−0.36964 (18)	0.59583 (15)	0.0439 (6)
C4	0.6909 (3)	−0.37093 (19)	0.63708 (16)	0.0470 (6)
C5	0.6343 (3)	−0.2791 (2)	0.64957 (16)	0.0506 (6)
C6	0.6642 (2)	−0.18277 (19)	0.61995 (15)	0.0433 (6)
C7	0.8447 (3)	−0.4689 (2)	0.58432 (18)	0.0607 (8)
C8	0.7884 (2)	−0.08128 (17)	0.54186 (14)	0.0386 (5)
C9	0.89235 (18)	0.16430 (17)	0.57434 (13)	0.0346 (5)
C10	0.9420 (3)	0.11372 (19)	0.64906 (15)	0.0450 (6)
C11	1.0408 (3)	0.1582 (3)	0.69911 (16)	0.0571 (7)
C12	1.0854 (3)	0.2507 (3)	0.67599 (17)	0.0551 (7)
C13	1.0326 (3)	0.3013 (2)	0.60202 (17)	0.0501 (6)
C14	0.9348 (2)	0.25843 (19)	0.54964 (15)	0.0422 (6)
C15	0.65558 (19)	0.20356 (16)	0.53852 (13)	0.0340 (5)
C16	0.6462 (2)	0.30164 (19)	0.49989 (15)	0.0441 (6)
C17	0.5733 (3)	0.3747 (2)	0.52257 (19)	0.0568 (7)
C18	0.5112 (3)	0.3506 (3)	0.58164 (18)	0.0561 (7)
C19	0.5241 (3)	0.2537 (3)	0.62010 (19)	0.0583 (7)
C20	0.5974 (3)	0.1782 (2)	0.59955 (16)	0.0486 (6)
C21	0.8615 (2)	0.1007 (2)	0.38780 (15)	0.0442 (6)
C22	0.8773 (3)	0.1727 (3)	0.31817 (19)	0.0669 (9)
C23	0.6442 (3)	0.1176 (3)	0.35908 (16)	0.0513 (7)
C24	0.6170 (3)	0.0048 (3)	0.3314 (3)	0.0791 (11)
B1	0.7324 (3)	0.0342 (3)	0.82280 (18)	0.0553 (8)
H1	0.8689	−0.2712	0.5365	0.0500*
H2	0.6685	−0.4362	0.6573	0.0564*
H3	0.5742	−0.2820	0.6788	0.0607*
H4	0.6256	−0.1197	0.6291	0.0520*
H5	0.9276	−0.4539	0.5980	0.0729*
H6	0.8206	−0.4927	0.5258	0.0729*
H7	0.8283	−0.5245	0.6217	0.0729*
H8	0.9096	0.0508	0.6655	0.0540*
H9	1.0782	0.1242	0.7500	0.0685*
H10	1.1529	0.2802	0.7111	0.0661*
H11	1.0635	0.3658	0.5870	0.0601*
H12	0.8981	0.2923	0.4985	0.0506*
H13	0.6887	0.3181	0.4591	0.0529*
H14	0.5656	0.4427	0.4972	0.0682*
H15	0.4596	0.4011	0.5955	0.0674*
H16	0.4823	0.2380	0.6614	0.0699*
H17	0.6072	0.1112	0.6266	0.0583*
H18	0.8519	0.0270	0.3669	0.0530*
H19	0.9310	0.1036	0.4347	0.0530*
H20	0.8103	0.1669	0.2705	0.0803*
H21	0.9470	0.1522	0.3001	0.0803*
H22	0.8849	0.2459	0.3384	0.0803*
H23	0.6424	0.1615	0.3086	0.0616*
H24	0.5829	0.1439	0.3856	0.0616*
H25	0.6226	−0.0403	0.3810	0.0949*
H26	0.6720	−0.0196	0.2994	0.0949*
H27	0.5386	0.0010	0.2959	0.0949*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0269 (4)	0.0320 (3)	0.0363 (3)	0.00407 (18)	0.0077 (3)	0.00063 (17)
F1	0.136 (3)	0.150 (3)	0.239 (4)	−0.025 (3)	0.099 (3)	0.069 (3)
F2	0.137 (3)	0.164 (3)	0.117 (2)	0.079 (3)	−0.0370 (18)	−0.0409 (18)
F3	0.1131 (19)	0.1178 (19)	0.0745 (13)	0.0108 (15)	−0.0176 (13)	−0.0239 (13)
F4	0.169 (3)	0.155 (3)	0.0724 (14)	−0.023 (2)	0.0645 (16)	−0.0245 (14)
O1	0.0398 (10)	0.0411 (9)	0.0768 (12)	0.0064 (8)	0.0267 (9)	0.0050 (8)
N1	0.0344 (11)	0.0334 (9)	0.0460 (10)	0.0037 (8)	0.0119 (8)	0.0034 (8)
N2	0.0300 (11)	0.0442 (10)	0.0358 (10)	0.0043 (8)	0.0084 (8)	−0.0016 (8)
C1	0.0322 (13)	0.0346 (11)	0.0416 (12)	0.0019 (9)	0.0028 (9)	0.0009 (9)
C2	0.0403 (14)	0.0384 (12)	0.0449 (12)	0.0039 (10)	0.0071 (10)	−0.0019 (9)
C3	0.0493 (16)	0.0352 (11)	0.0411 (12)	0.0009 (10)	−0.0015 (11)	−0.0018 (9)
C4	0.0498 (16)	0.0385 (12)	0.0468 (13)	−0.0060 (11)	−0.0007 (11)	0.0071 (10)
C5	0.0427 (15)	0.0540 (15)	0.0554 (15)	−0.0018 (12)	0.0119 (12)	0.0100 (12)
C6	0.0366 (14)	0.0422 (12)	0.0502 (13)	0.0039 (10)	0.0083 (10)	0.0051 (10)
C7	0.082 (3)	0.0374 (13)	0.0606 (16)	0.0068 (13)	0.0114 (15)	−0.0022 (11)
C8	0.0308 (13)	0.0363 (11)	0.0479 (12)	0.0037 (10)	0.0076 (10)	0.0005 (10)
C9	0.0270 (12)	0.0387 (11)	0.0375 (11)	0.0049 (9)	0.0062 (9)	−0.0046 (9)
C10	0.0457 (15)	0.0469 (13)	0.0393 (12)	0.0078 (11)	0.0037 (11)	0.0011 (10)
C11	0.0537 (17)	0.0652 (17)	0.0438 (13)	0.0101 (14)	−0.0059 (12)	−0.0045 (12)
C12	0.0353 (15)	0.0698 (17)	0.0541 (15)	0.0023 (13)	−0.0022 (11)	−0.0213 (13)
C13	0.0371 (14)	0.0526 (14)	0.0613 (15)	−0.0059 (12)	0.0133 (12)	−0.0128 (12)
C14	0.0338 (13)	0.0449 (12)	0.0474 (13)	−0.0001 (10)	0.0084 (10)	0.0007 (10)
C15	0.0274 (12)	0.0348 (11)	0.0391 (11)	0.0064 (9)	0.0063 (9)	−0.0020 (8)
C16	0.0416 (14)	0.0417 (12)	0.0502 (13)	0.0111 (11)	0.0135 (11)	0.0063 (10)
C17	0.0575 (18)	0.0437 (14)	0.0709 (18)	0.0203 (12)	0.0184 (14)	0.0080 (12)
C18	0.0508 (17)	0.0512 (15)	0.0692 (17)	0.0179 (13)	0.0196 (14)	−0.0075 (13)
C19	0.0566 (18)	0.0604 (16)	0.0676 (17)	0.0101 (14)	0.0343 (14)	−0.0019 (13)
C20	0.0500 (16)	0.0442 (13)	0.0577 (14)	0.0097 (12)	0.0251 (12)	0.0051 (11)
C21	0.0356 (14)	0.0551 (14)	0.0459 (13)	0.0042 (11)	0.0177 (11)	−0.0033 (10)
C22	0.066 (2)	0.084 (2)	0.0606 (17)	0.0052 (17)	0.0341 (16)	0.0114 (15)
C23	0.0342 (15)	0.0780 (19)	0.0399 (13)	0.0003 (12)	0.0050 (10)	−0.0072 (11)
C24	0.064 (2)	0.099 (3)	0.0704 (19)	−0.0223 (19)	0.0087 (16)	−0.0359 (18)
B1	0.067 (3)	0.0594 (18)	0.0407 (14)	0.0017 (16)	0.0144 (14)	−0.0027 (13)

Geometric parameters (Å, º) top

S1—N1	1.551 (2)	C19—C20	1.388 (5)
S1—N2	1.619 (2)	C21—C22	1.503 (5)
S1—C9	1.777 (2)	C23—C24	1.509 (5)
S1—C15	1.762 (3)	C2—H1	0.950
F1—B1	1.339 (6)	C4—H2	0.950
F2—B1	1.358 (5)	C5—H3	0.950
F3—B1	1.375 (4)	C6—H4	0.950
F4—B1	1.320 (5)	C7—H5	0.980
O1—C8	1.224 (4)	C7—H6	0.980
N1—C8	1.395 (3)	C7—H7	0.980
N2—C21	1.503 (4)	C10—H8	0.950
N2—C23	1.488 (3)	C11—H9	0.950
C1—C2	1.392 (4)	C12—H10	0.950
C1—C6	1.391 (4)	C13—H11	0.950
C1—C8	1.484 (4)	C14—H12	0.950
C2—C3	1.388 (4)	C16—H13	0.950
C3—C4	1.377 (5)	C17—H14	0.950
C3—C7	1.513 (4)	C18—H15	0.950
C4—C5	1.382 (4)	C19—H16	0.950
C5—C6	1.388 (4)	C20—H17	0.950
C9—C10	1.383 (3)	C21—H18	0.990
C9—C14	1.390 (4)	C21—H19	0.990
C10—C11	1.387 (4)	C22—H20	0.980
C11—C12	1.374 (5)	C22—H21	0.980
C12—C13	1.383 (4)	C22—H22	0.980
C13—C14	1.386 (4)	C23—H23	0.990
C15—C16	1.384 (4)	C23—H24	0.990
C15—C20	1.380 (4)	C24—H25	0.980
C16—C17	1.378 (4)	C24—H26	0.980
C17—C18	1.382 (5)	C24—H27	0.980
C18—C19	1.368 (4)

N1—S1—N2	122.65 (10)	C6—C5—H3	119.615
N1—S1—C9	114.85 (10)	C1—C6—H4	120.640
N1—S1—C15	103.35 (11)	C5—C6—H4	120.642
N2—S1—C9	104.95 (11)	C3—C7—H5	109.464
N2—S1—C15	104.96 (10)	C3—C7—H6	109.466
C9—S1—C15	104.17 (10)	C3—C7—H7	109.465
S1—N1—C8	116.62 (17)	H5—C7—H6	109.487
S1—N2—C21	119.21 (14)	H5—C7—H7	109.474
S1—N2—C23	115.20 (17)	H6—C7—H7	109.470
C21—N2—C23	115.73 (19)	C9—C10—H8	121.216
C2—C1—C6	119.7 (3)	C11—C10—H8	121.202
C2—C1—C8	117.8 (3)	C10—C11—H9	119.576
C6—C1—C8	122.5 (2)	C12—C11—H9	119.586
C1—C2—C3	121.5 (3)	C11—C12—H10	119.725
C2—C3—C4	118.1 (3)	C13—C12—H10	119.724
C2—C3—C7	120.1 (3)	C12—C13—H11	119.844
C4—C3—C7	121.8 (3)	C14—C13—H11	119.836
C3—C4—C5	121.2 (3)	C9—C14—H12	121.085
C4—C5—C6	120.8 (3)	C13—C14—H12	121.089
C1—C6—C5	118.7 (3)	C15—C16—H13	121.107
O1—C8—N1	123.5 (2)	C17—C16—H13	121.105
O1—C8—C1	122.3 (2)	C16—C17—H14	119.482
N1—C8—C1	114.2 (3)	C18—C17—H14	119.470
S1—C9—C10	116.40 (18)	C17—C18—H15	120.093
S1—C9—C14	120.16 (16)	C19—C18—H15	120.090
C10—C9—C14	122.8 (2)	C18—C19—H16	119.526
C9—C10—C11	117.6 (3)	C20—C19—H16	119.523
C10—C11—C12	120.8 (3)	C15—C20—H17	121.092
C11—C12—C13	120.6 (3)	C19—C20—H17	121.089
C12—C13—C14	120.3 (3)	N2—C21—H18	109.466
C9—C14—C13	117.8 (2)	N2—C21—H19	109.463
S1—C15—C16	118.3 (2)	C22—C21—H18	109.463
S1—C15—C20	118.76 (17)	C22—C21—H19	109.464
C16—C15—C20	122.5 (3)	H18—C21—H19	108.058
C15—C16—C17	117.8 (3)	C21—C22—H20	109.479
C16—C17—C18	121.0 (3)	C21—C22—H21	109.469
C17—C18—C19	119.8 (3)	C21—C22—H22	109.477
C18—C19—C20	121.0 (3)	H20—C22—H21	109.466
C15—C20—C19	117.8 (3)	H20—C22—H22	109.469
N2—C21—C22	110.9 (3)	H21—C22—H22	109.467
N2—C23—C24	114.7 (3)	N2—C23—H23	108.586
F1—B1—F2	112.1 (4)	N2—C23—H24	108.588
F1—B1—F3	106.6 (3)	C24—C23—H23	108.594
F1—B1—F4	108.6 (4)	C24—C23—H24	108.588
F2—B1—F3	107.8 (3)	H23—C23—H24	107.553
F2—B1—F4	111.8 (3)	C23—C24—H25	109.471
F3—B1—F4	109.7 (4)	C23—C24—H26	109.469
C1—C2—H1	119.276	C23—C24—H27	109.466
C3—C2—H1	119.262	H25—C24—H26	109.476
C3—C4—H2	119.372	H25—C24—H27	109.474
C5—C4—H2	119.381	H26—C24—H27	109.471
C4—C5—H3	119.624

N1—S1—N2—C21	−85.43 (16)	C2—C1—C8—O1	−3.4 (3)
N1—S1—N2—C23	58.94 (17)	C2—C1—C8—N1	175.71 (17)
N2—S1—N1—C8	62.03 (16)	C8—C1—C2—C3	−179.78 (16)
N1—S1—C9—C10	−9.7 (2)	C6—C1—C8—O1	175.96 (19)
N1—S1—C9—C14	178.86 (15)	C6—C1—C8—N1	−4.9 (3)
C9—S1—N1—C8	−67.35 (15)	C8—C1—C6—C5	179.28 (17)
N1—S1—C15—C16	−165.52 (13)	C1—C2—C3—C4	0.5 (3)
N1—S1—C15—C20	21.46 (16)	C1—C2—C3—C7	−178.65 (17)
C15—S1—N1—C8	179.88 (12)	C2—C3—C4—C5	−1.2 (4)
N2—S1—C9—C10	−147.38 (15)	C7—C3—C4—C5	177.9 (2)
N2—S1—C9—C14	41.21 (19)	C3—C4—C5—C6	0.7 (4)
C9—S1—N2—C21	48.02 (16)	C4—C5—C6—C1	0.6 (4)
C9—S1—N2—C23	−167.61 (12)	S1—C9—C10—C11	−173.55 (16)
N2—S1—C15—C16	−35.93 (16)	S1—C9—C14—C13	172.18 (16)
N2—S1—C15—C20	151.06 (14)	C10—C9—C14—C13	1.3 (4)
C15—S1—N2—C21	157.51 (13)	C14—C9—C10—C11	−2.4 (4)
C15—S1—N2—C23	−58.13 (15)	C9—C10—C11—C12	1.8 (4)
C9—S1—C15—C16	74.12 (15)	C10—C11—C12—C13	−0.2 (5)
C9—S1—C15—C20	−98.89 (15)	C11—C12—C13—C14	−0.9 (5)
C15—S1—C9—C10	102.56 (16)	C12—C13—C14—C9	0.3 (4)
C15—S1—C9—C14	−68.85 (18)	S1—C15—C16—C17	−174.46 (13)
S1—N1—C8—O1	−2.3 (3)	S1—C15—C20—C19	174.92 (14)
S1—N1—C8—C1	178.56 (11)	C16—C15—C20—C19	2.2 (4)
S1—N2—C21—C22	−148.33 (13)	C20—C15—C16—C17	−1.7 (3)
S1—N2—C23—C24	−85.0 (3)	C15—C16—C17—C18	−0.3 (4)
C21—N2—C23—C24	60.7 (3)	C16—C17—C18—C19	1.7 (4)
C23—N2—C21—C22	67.5 (3)	C17—C18—C19—C20	−1.2 (4)
C2—C1—C6—C5	−1.4 (3)	C18—C19—C20—C15	−0.7 (4)
C6—C1—C2—C3	0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H6···F3ⁱ	0.98	2.50	3.446 (4)	163
C10—H8···F4	0.95	2.48	3.202 (5)	133
C14—H12···F3ⁱⁱ	0.95	2.51	3.433 (3)	165
C16—H13···F2ⁱⁱ	0.95	2.61	3.367 (4)	137
C16—H13···F3ⁱⁱ	0.95	2.55	3.450 (4)	158
C18—H15···F1ⁱⁱⁱ	0.95	2.33	3.200 (5)	150

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

Acknowledgements

The authors are grateful to the Department of Applied Chemistry, Faculty of Engineering, University of Toyama for the provision of laboratory facilities and to the Center for Environmental Conservation and Research Safety, University of Toyama, Japan, for providing facilities for single-crystal X-ray analysis.

Funding information

This work was supported in part by the Japan Society for the Promotion of Science, JSPS (award No. P11336).

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