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ISSN: 2414-3146

S,S-Di­phenyl-S-pyrrolidino­imino­sulfonium perchlorate

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 6 August 2017; accepted 31 August 2017; online 15 September 2017)

The asymmetric unit of the title salt, C16H19N2S+·ClO4, consists of two crystallographically independent cations and anions. In the salt, protonation occurs at the nitrile N atom attached to the S atom of the corresponding λ6-sulfane­nitrile. The structures of the two independent cations are almost the same and the configuration around the S atom is a slightly distorted tetra­hedral geometry, with two S—N bonds and two S—C bonds. The S—N(pyrrolidine) and S=N bond lengths are 1.6216 (18) and 1.503 (2) Å, respectively, for one cation, and 1.6236 (19) and 1.502 (2) Å, respectively, for the other. The dihedral angles between the two phenyl rings in the cations are 76.61 (9) and 76.42 (9)°. There are N—H⋯O hydrogen bonds, which link the cation and the anion. The cation–anion pairs are further linked by C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional network.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The chemistry of heteroatom-substituted sulfonium salts (hetero­sulfonium salts) is very inter­esting because of their anomalous reactivity (Oae et al., 1981[Oae, S., Numata, T. & Yoshimura, T. (1981). The Chemistry of the Sulphonium Group, Part 2, edited by C. J. M. Stirling, p. 571. New York: John Wiley & Sons.]). Meanwhile, only a few sulfur(VI) sulfonium compounds, such as oxo­sulfonium salts, have been reported to date (Mori et al., 1990[Mori, M., Takeuchi, H., Minato, H., Kobayashi, M., Yoshida, M., Matsuyama, H. & Kamigata, N. (1990). Phosphorus Sulfur Silicon, 47, 157-164.]). Furthermore, imino­sulfonium salts belong to the isoelectronic compounds of the oxo­sulfonium salts and are very rare. Previously, we prepared S,S,S-tri­phenyl­sulfane­nitrile bearing an S≡N triple bond and found that its N atom has a nucleophilic character (Yoshimura et al., 1997[Yoshimura, T., Hamada, K., Imado, M., Hamata, K., Tomoda, T., Fujii, T., Morita, H., Shimasaki, S., Ono, S., Tsukurimichi, E., Furukawa, N. & Kimura, T. (1997). J. Org. Chem. 62, 3802-3803.]) and thus reported the preparation of imino­sulfonium salts bearing three carbon ligands by its alkyl­ation or neutralization (Yoshimura et al., 1998[Yoshimura, T., Fujii, T., Hamata, K., Imado, M., Morita, H., Ono, S. & Horn, E. (1998). Chem. Lett. 27, 1013-1014.]). However, imino­sulfonium salts bearing two carbons and one amino ligand are also very rare. Furthermore, we reported that the reaction of S,S-diaryl-S-fluoro­sulfane­nitrile with cyclic secondary amines afforded the corresponding amino­sulfane­nitriles (Yoshimura, Kita et al., 1992[Yoshimura, T., Kita, H., Takeuchi, K., Takata, E., Hasegawa, K., Shimasaki, C. & Tsukurimichi, E. (1992). Chem. Lett. 21, 1433-1436.]; Yoshimura, Takata et al., 1992[Yoshimura, T., Takata, E., Miyake, T., Shimasaki, C., Hasegawa, K. & Tsukurimichi, E. (1992). Chem. Lett. 21, 2213-2216.]), though the corresponding pyrrolidinosulfane­nitrile was an impure oily material and thus its identification remained ambiguous. The crystal structure of the title compound, which is now successfully resolved, is a precursor of the sulfane­nitrile.

The mol­ecular structure of the title compound is illustrated in Fig. 1[link]. The S1—N1(pyrrolidine) and S1—N2(NH) bond lengths in one cation are 1.6216 (18) and 1.503 (2) Å, respectively. The corresponding bond lengths of the other cation, S2—N3(pyrrolidine) and S2—N4(NH), are 1.6236 (19) and 1.502 (2) Å, respectively. The S1—N2 and S2—N4 bond lengths are significantly longer than the S≡N triple bond of tri­phenyl­sulfane­nitrile [1.462 (3) Å; Yoshimura et al., 1997[Yoshimura, T., Hamada, K., Imado, M., Hamata, K., Tomoda, T., Fujii, T., Morita, H., Shimasaki, S., Ono, S., Tsukurimichi, E., Furukawa, N. & Kimura, T. (1997). J. Org. Chem. 62, 3802-3803.]] and close to the double bond of S,S-di­methyl­sulfonedi­imine [1.533 (2) Å, electron diffraction study; Oberhammer & Zeil, 1969[Oberhammer, H. & Zeil, W. (1969). Z. Naturforsch. Teil A, 24, 1612-1616.]] and those of S1—N1 and S2—N3 are close to the S—N single bond of a sulfonedi­imino­sulfonium salt [1.599 (3) Å; Ohkubo et al., 1997[Ohkubo, M., Fujii, T., Ono, S., Morita, H., Yoshimura, T., Ernst, H. & Sato, S. (1997). Chem. Lett. 26, 153-154.]]. There are N—H⋯O hydrogen bonds involving the perchlorate counter-anion. In the extended structure, the anions are linked through weak C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional network (Table 1[link] and Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H19⋯O2i 0.76 (4) 2.34 (4) 3.057 (4) 159 (4)
N4—H38⋯O8ii 0.79 (3) 2.16 (3) 2.952 (4) 173 (3)
C2—H1⋯O1 0.95 2.58 3.531 (3) 178
C10—H8⋯O7iii 0.95 2.56 3.453 (4) 157
C12—H10⋯O1 0.95 2.43 3.379 (4) 174
C16—H18⋯O4i 0.99 2.58 3.392 (4) 139
C18—H20⋯O6 0.95 2.47 3.362 (3) 156
C25—H26⋯O3iv 0.95 2.57 3.512 (5) 171
C29—H30⋯O5ii 0.99 2.50 3.344 (3) 142
C28—H29⋯N4v 0.95 2.58 3.401 (4) 145
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) [x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iv) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (v) -x, -y, -z+1.
[Figure 1]
Figure 1
The asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
A packing view of the title compound, showing N—H⋯O, C—H⋯O, and C—H⋯N hydrogen bonds (dashed lines).

Synthesis and crystallization

Fluoro­diphenyl-λ6-sulfane­nitrile (Yoshimura et al., 1998[Yoshimura, T., Fujii, T., Hamata, K., Imado, M., Morita, H., Ono, S. & Horn, E. (1998). Chem. Lett. 27, 1013-1014.]) (219 mg, 0.91 mmol) was treated with an excess of pyrrolidine (512 mg, 7.2 mmol) at 303 K for 8 h. The excess pyrrolidine was removed in a vacuum and the residue was dissolved in CHCl3 (20 ml). The solution was then washed with water (3 × 30 ml), dried over anhydrous MgSO4 and concentrated under reduced pressure to give the corresponding S,S-diphenyl-S-pyrrolidino-λ6-sulfane­nitrile (yield: 226 mg, 92%) as a colourless oil. HClO4 (183 mg, 1.8 mmol) was added to the ice-cooled oily pyrrolidino-λ6-sulfane­nitrile to give the corresponding title compound (yield: 250 mg, 74%) as a solid. Single crystals were obtained from a THF/hexane (1:1 v/v) solution (m.p. 414–415 K).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula C16H19N2S+·ClO4
Mr 370.85
Crystal system, space group Monoclinic, P21/c
Temperature (K) 173
a, b, c (Å) 13.4430 (3), 15.9737 (3), 17.6478 (4)
β (°) 113.0241 (7)
V3) 3487.71 (12)
Z 8
Radiation type Cu Kα
μ (mm−1) 3.26
Crystal size (mm) 0.55 × 0.47 × 0.12
 
Data collection
Diffractometer Rigaku R-AXIS RAPID
Absorption correction Multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.])
Tmin, Tmax 0.549, 0.676
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections 40289, 6302, 5448
Rint 0.088
(sin θ/λ)max−1) 0.602
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.149, 1.12
No. of reflections 6302
No. of parameters 441
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.55, −0.32
Computer programs: RAPID-AUTO (Rigaku, 2001[Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]), SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and CrystalStructure (Rigaku, 2010[Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan.]).

Structural data


Computing details top

Cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: 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,S-Diphenyl-S-pyrrolidinoiminosulfonium perchlorate top
Crystal data top
C16H19N2S+·ClO4F(000) = 1552.00
Mr = 370.85Dx = 1.412 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybcCell parameters from 32602 reflections
a = 13.4430 (3) Åθ = 3.5–68.3°
b = 15.9737 (3) ŵ = 3.26 mm1
c = 17.6478 (4) ÅT = 173 K
β = 113.0241 (7)°Prism, colorless
V = 3487.71 (12) Å30.55 × 0.47 × 0.12 mm
Z = 8
Data collection top
Rigaku R-AXIS RAPID
diffractometer
5448 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.000 pixels mm-1Rint = 0.088
ω scansθmax = 68.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1616
Tmin = 0.549, Tmax = 0.676k = 1919
40289 measured reflectionsl = 2121
6302 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0943P)2 + 0.1549P]
where P = (Fo2 + 2Fc2)/3
6302 reflections(Δ/σ)max = 0.001
441 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = 0.32 e Å3
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
xyzUiso*/Ueq
Cl10.38944 (5)0.11435 (3)0.82405 (4)0.05096 (19)
Cl20.14167 (4)0.38569 (3)0.15363 (3)0.04201 (17)
S10.36462 (4)0.40529 (3)0.66582 (3)0.03120 (16)
S20.08538 (4)0.10611 (3)0.34805 (3)0.02793 (15)
O10.42043 (15)0.19964 (10)0.84419 (10)0.0561 (5)
O20.4479 (2)0.06208 (12)0.89219 (13)0.0890 (7)
O30.2754 (2)0.10696 (12)0.80241 (19)0.1026 (9)
O40.4133 (3)0.08960 (13)0.75582 (14)0.0900 (7)
O50.13271 (18)0.41880 (12)0.23112 (12)0.0768 (7)
O60.14848 (14)0.29633 (9)0.15370 (10)0.0536 (5)
O70.23833 (14)0.41859 (12)0.09070 (12)0.0683 (6)
O80.05282 (16)0.40968 (12)0.13368 (15)0.0802 (7)
N10.40788 (14)0.39352 (10)0.76479 (10)0.0328 (4)
N20.35139 (18)0.48934 (12)0.62469 (13)0.0479 (5)
N30.11238 (14)0.11995 (10)0.25085 (10)0.0342 (4)
N40.10848 (16)0.02588 (11)0.38252 (11)0.0390 (5)
C10.23451 (16)0.35996 (13)0.63014 (13)0.0370 (5)
C20.21724 (18)0.28907 (13)0.66878 (15)0.0438 (6)
C30.1160 (2)0.25251 (17)0.63550 (18)0.0596 (8)
C40.0359 (2)0.2863 (3)0.56709 (19)0.0720 (10)
C50.0552 (2)0.3564 (3)0.53012 (18)0.0753 (10)
C60.1549 (2)0.39426 (17)0.56089 (15)0.0561 (7)
C70.44895 (15)0.33417 (12)0.64093 (11)0.0310 (5)
C80.47267 (17)0.35375 (14)0.57329 (13)0.0396 (5)
C90.53268 (17)0.29701 (15)0.54894 (14)0.0462 (6)
C100.56734 (17)0.22232 (15)0.59166 (14)0.0466 (6)
C110.54229 (17)0.20434 (13)0.65898 (14)0.0431 (6)
C120.48232 (16)0.25963 (12)0.68421 (12)0.0359 (5)
C130.34319 (18)0.43232 (16)0.80815 (13)0.0477 (6)
C140.4255 (2)0.43849 (19)0.89608 (14)0.0585 (7)
C150.5300 (2)0.45794 (16)0.88720 (15)0.0546 (7)
C160.52663 (17)0.40682 (14)0.81456 (13)0.0417 (6)
C170.16429 (15)0.18334 (11)0.37007 (11)0.0303 (5)
C180.17600 (17)0.26117 (12)0.33235 (12)0.0378 (5)
C190.23279 (17)0.32256 (13)0.35414 (13)0.0418 (6)
C200.27669 (17)0.30589 (13)0.41160 (13)0.0412 (5)
C210.26307 (17)0.22830 (13)0.44834 (13)0.0403 (5)
C220.20674 (15)0.16573 (12)0.42794 (12)0.0341 (5)
C230.05042 (16)0.14216 (12)0.39332 (12)0.0334 (5)
C240.0867 (2)0.20851 (14)0.36060 (15)0.0479 (6)
C250.1929 (3)0.23469 (18)0.4032 (2)0.0669 (9)
C260.2576 (2)0.1960 (2)0.4756 (2)0.0732 (10)
C270.2200 (2)0.13014 (19)0.50700 (17)0.0636 (8)
C280.11512 (18)0.10252 (14)0.46578 (14)0.0439 (6)
C290.03949 (19)0.08011 (14)0.21546 (13)0.0443 (6)
C300.1147 (3)0.03031 (15)0.14368 (15)0.0570 (7)
C310.2202 (3)0.07948 (17)0.11491 (15)0.0598 (7)
C320.22891 (19)0.10621 (14)0.19396 (13)0.0452 (6)
H10.27290.26650.71630.0525*
H20.10170.20360.66020.0716*
H30.03350.26070.54530.0864*
H40.00080.37900.48280.0904*
H50.16880.44270.53530.0673*
H60.44850.40480.54430.0476*
H70.55010.30930.50290.0554*
H80.60820.18360.57470.0559*
H90.56660.15340.68810.0517*
H100.46430.24710.72990.0430*
H110.28150.39630.80440.0572*
H120.31580.48830.78540.0572*
H130.40610.48370.92620.0702*
H140.43070.38500.92570.0702*
H150.59270.44180.93750.0655*
H160.53500.51840.87690.0655*
H170.56430.35270.83270.0500*
H180.56070.43740.78220.0500*
H190.407 (3)0.5079 (19)0.633 (2)0.077 (12)*
H200.14590.27200.29280.0454*
H210.24160.37640.32950.0502*
H220.31630.34800.42570.0495*
H230.29270.21760.48820.0484*
H240.19760.11210.45310.0409*
H250.04090.23510.31110.0574*
H260.22100.27950.38210.0803*
H270.32950.21530.50430.0879*
H280.26570.10380.55670.0764*
H290.08780.05710.48670.0527*
H300.01410.04320.25640.0532*
H310.00070.12310.19710.0532*
H320.12470.02700.16090.0684*
H330.08680.02660.09950.0684*
H340.21720.12870.08170.0717*
H350.28210.04380.08170.0717*
H360.26270.06190.21520.0542*
H370.27140.15840.18630.0542*
H380.069 (3)0.0082 (16)0.3762 (17)0.065 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0651 (5)0.0311 (3)0.0662 (4)0.0069 (3)0.0360 (4)0.0044 (3)
Cl20.0461 (4)0.0330 (3)0.0509 (4)0.0072 (2)0.0232 (3)0.0009 (2)
S10.0299 (3)0.0265 (3)0.0337 (3)0.00179 (17)0.0086 (2)0.00152 (17)
S20.0299 (3)0.0242 (3)0.0285 (3)0.00118 (17)0.0102 (2)0.00214 (16)
O10.0770 (13)0.0362 (9)0.0530 (10)0.0018 (8)0.0232 (9)0.0014 (7)
O20.138 (2)0.0565 (12)0.0865 (15)0.0370 (13)0.0589 (15)0.0311 (11)
O30.0711 (16)0.0634 (14)0.182 (3)0.0075 (11)0.0584 (17)0.0055 (15)
O40.150 (3)0.0563 (13)0.0881 (16)0.0058 (14)0.0734 (16)0.0106 (11)
O50.1163 (19)0.0560 (12)0.0627 (13)0.0213 (12)0.0402 (13)0.0161 (10)
O60.0725 (12)0.0332 (9)0.0582 (10)0.0063 (8)0.0289 (9)0.0039 (7)
O70.0571 (12)0.0597 (12)0.0802 (14)0.0104 (9)0.0182 (10)0.0063 (10)
O80.0650 (13)0.0598 (12)0.136 (2)0.0101 (10)0.0613 (14)0.0111 (12)
N10.0285 (9)0.0340 (9)0.0330 (9)0.0021 (7)0.0089 (8)0.0029 (7)
N20.0505 (13)0.0327 (10)0.0570 (13)0.0058 (9)0.0172 (10)0.0099 (9)
N30.0407 (10)0.0302 (9)0.0289 (9)0.0043 (7)0.0104 (8)0.0018 (7)
N40.0488 (11)0.0260 (9)0.0473 (11)0.0029 (8)0.0241 (9)0.0044 (8)
C10.0271 (11)0.0416 (12)0.0392 (11)0.0017 (9)0.0097 (9)0.0094 (9)
C20.0368 (12)0.0384 (12)0.0561 (14)0.0049 (9)0.0182 (11)0.0091 (10)
C30.0466 (15)0.0581 (16)0.083 (2)0.0187 (12)0.0352 (15)0.0302 (14)
C40.0325 (14)0.103 (3)0.078 (2)0.0193 (15)0.0188 (14)0.0517 (19)
C50.0339 (15)0.120 (3)0.0557 (18)0.0016 (16)0.0003 (13)0.0209 (18)
C60.0379 (14)0.0797 (19)0.0396 (13)0.0098 (12)0.0032 (11)0.0011 (12)
C70.0259 (10)0.0314 (10)0.0327 (10)0.0020 (8)0.0081 (8)0.0032 (8)
C80.0318 (11)0.0461 (12)0.0380 (11)0.0065 (9)0.0104 (9)0.0006 (9)
C90.0337 (12)0.0652 (16)0.0421 (12)0.0069 (11)0.0175 (10)0.0103 (11)
C100.0297 (11)0.0565 (15)0.0523 (14)0.0005 (10)0.0146 (10)0.0183 (11)
C110.0368 (12)0.0379 (12)0.0470 (13)0.0034 (9)0.0083 (10)0.0055 (10)
C120.0356 (11)0.0313 (10)0.0383 (11)0.0013 (9)0.0118 (9)0.0017 (8)
C130.0424 (13)0.0579 (15)0.0415 (13)0.0049 (11)0.0150 (10)0.0121 (11)
C140.0555 (16)0.0770 (19)0.0398 (13)0.0022 (14)0.0152 (12)0.0139 (12)
C150.0484 (14)0.0570 (15)0.0456 (13)0.0034 (12)0.0045 (11)0.0115 (11)
C160.0314 (12)0.0464 (13)0.0388 (12)0.0005 (9)0.0046 (10)0.0048 (9)
C170.0291 (10)0.0257 (9)0.0306 (10)0.0017 (8)0.0057 (8)0.0018 (8)
C180.0467 (13)0.0309 (10)0.0354 (11)0.0039 (9)0.0157 (10)0.0029 (8)
C190.0496 (13)0.0303 (11)0.0396 (12)0.0101 (9)0.0109 (10)0.0023 (9)
C200.0375 (12)0.0427 (12)0.0379 (11)0.0098 (10)0.0087 (9)0.0072 (9)
C210.0349 (11)0.0460 (13)0.0404 (12)0.0034 (10)0.0151 (10)0.0017 (9)
C220.0291 (10)0.0350 (11)0.0360 (11)0.0015 (8)0.0105 (9)0.0008 (8)
C230.0294 (11)0.0324 (10)0.0381 (11)0.0004 (8)0.0129 (9)0.0062 (8)
C240.0490 (14)0.0411 (12)0.0591 (15)0.0107 (11)0.0273 (12)0.0083 (11)
C250.0617 (18)0.0554 (17)0.098 (3)0.0209 (14)0.0467 (18)0.0279 (16)
C260.0333 (14)0.080 (2)0.099 (3)0.0082 (14)0.0181 (15)0.0472 (19)
C270.0354 (14)0.0767 (19)0.0609 (17)0.0126 (13)0.0005 (12)0.0243 (14)
C280.0369 (12)0.0514 (14)0.0396 (13)0.0092 (10)0.0108 (10)0.0048 (10)
C290.0582 (15)0.0432 (13)0.0377 (12)0.0010 (11)0.0255 (11)0.0006 (10)
C300.0808 (19)0.0502 (14)0.0477 (14)0.0105 (13)0.0333 (14)0.0167 (11)
C310.0714 (18)0.0594 (16)0.0364 (13)0.0020 (14)0.0079 (12)0.0033 (11)
C320.0417 (13)0.0435 (13)0.0359 (12)0.0060 (10)0.0005 (10)0.0037 (9)
Geometric parameters (Å, º) top
Cl1—O11.4283 (17)C25—C261.380 (5)
Cl1—O21.422 (2)C26—C271.375 (5)
Cl1—O31.432 (3)C27—C281.381 (4)
Cl1—O41.418 (3)C29—C301.503 (3)
Cl2—O51.427 (3)C30—C311.524 (4)
Cl2—O61.4304 (16)C31—C321.507 (4)
Cl2—O71.4385 (17)N2—H190.76 (4)
Cl2—O81.424 (3)N4—H380.79 (3)
S1—N11.6216 (18)C2—H10.950
S1—N21.503 (2)C3—H20.950
S1—C11.766 (2)C4—H30.950
S1—C71.777 (3)C5—H40.950
S2—N31.6236 (19)C6—H50.950
S2—N41.502 (2)C8—H60.950
S2—C171.767 (3)C9—H70.950
S2—C231.778 (2)C10—H80.950
N1—C131.499 (4)C11—H90.950
N1—C161.506 (3)C12—H100.950
N3—C291.495 (4)C13—H110.990
N3—C321.510 (3)C13—H120.990
C1—C21.387 (4)C14—H130.990
C1—C61.384 (3)C14—H140.990
C2—C31.383 (4)C15—H150.990
C3—C41.375 (4)C15—H160.990
C4—C51.371 (6)C16—H170.990
C5—C61.374 (4)C16—H180.990
C7—C81.386 (4)C18—H200.950
C7—C121.391 (3)C19—H210.950
C8—C91.389 (4)C20—H220.950
C9—C101.391 (4)C21—H230.950
C10—C111.386 (4)C22—H240.950
C11—C121.382 (4)C24—H250.950
C13—C141.516 (3)C25—H260.950
C14—C151.506 (5)C26—H270.950
C15—C161.506 (4)C27—H280.950
C17—C181.390 (3)C28—H290.950
C17—C221.380 (4)C29—H300.990
C18—C191.386 (4)C29—H310.990
C19—C201.384 (4)C30—H320.990
C20—C211.377 (3)C30—H330.990
C21—C221.384 (4)C31—H340.990
C23—C241.383 (4)C31—H350.990
C23—C281.387 (3)C32—H360.990
C24—C251.392 (4)C32—H370.990
O1—Cl1—O2109.80 (11)C3—C4—H3119.715
O1—Cl1—O3108.82 (12)C5—C4—H3119.711
O1—Cl1—O4109.67 (14)C4—C5—H4119.717
O2—Cl1—O3110.92 (17)C6—C5—H4119.703
O2—Cl1—O4108.71 (15)C1—C6—H5120.907
O3—Cl1—O4108.91 (18)C5—C6—H5120.905
O5—Cl2—O6110.52 (12)C7—C8—H6120.776
O5—Cl2—O7108.46 (13)C9—C8—H6120.779
O5—Cl2—O8111.89 (14)C8—C9—H7119.853
O6—Cl2—O7109.05 (10)C10—C9—H7119.868
O6—Cl2—O8109.21 (13)C9—C10—H8119.996
O7—Cl2—O8107.62 (13)C11—C10—H8119.983
N1—S1—N2123.26 (11)C10—C11—H9119.605
N1—S1—C1102.97 (11)C12—C11—H9119.606
N1—S1—C7101.38 (9)C7—C12—H10120.855
N2—S1—C1106.28 (11)C11—C12—H10120.865
N2—S1—C7114.71 (13)N1—C13—H11111.310
C1—S1—C7106.76 (10)N1—C13—H12111.306
N3—S2—N4123.22 (10)C14—C13—H11111.321
N3—S2—C17103.41 (9)C14—C13—H12111.316
N3—S2—C23101.34 (11)H11—C13—H12109.199
N4—S2—C17105.64 (12)C13—C14—H13110.935
N4—S2—C23115.65 (10)C13—C14—H14110.930
C17—S2—C23105.92 (10)C15—C14—H13110.942
S1—N1—C13117.82 (13)C15—C14—H14110.930
S1—N1—C16117.62 (17)H13—C14—H14108.947
C13—N1—C16109.77 (16)C14—C15—H15110.755
S2—N3—C29118.12 (13)C14—C15—H16110.747
S2—N3—C32115.33 (17)C16—C15—H15110.760
C29—N3—C32109.85 (17)C16—C15—H16110.748
S1—C1—C2119.48 (15)H15—C15—H16108.838
S1—C1—C6117.93 (19)N1—C16—H17110.914
C2—C1—C6122.5 (2)N1—C16—H18110.917
C1—C2—C3117.5 (2)C15—C16—H17110.915
C2—C3—C4120.7 (3)C15—C16—H18110.925
C3—C4—C5120.6 (3)H17—C16—H18108.947
C4—C5—C6120.6 (3)C17—C18—H20120.936
C1—C6—C5118.2 (3)C19—C18—H20120.940
S1—C7—C8116.90 (15)C18—C19—H21119.803
S1—C7—C12120.76 (18)C20—C19—H21119.799
C8—C7—C12122.2 (2)C19—C20—H22119.944
C7—C8—C9118.4 (2)C21—C20—H22119.940
C8—C9—C10120.3 (3)C20—C21—H23119.571
C9—C10—C11120.0 (3)C22—C21—H23119.571
C10—C11—C12120.8 (2)C17—C22—H24120.910
C7—C12—C11118.3 (3)C21—C22—H24120.918
N1—C13—C14102.28 (19)C23—C24—H25121.334
C13—C14—C15104.1 (3)C25—C24—H25121.334
C14—C15—C16105.0 (2)C24—C25—H26119.756
N1—C16—C15104.2 (2)C26—C25—H26119.751
S2—C17—C18118.99 (19)C25—C26—H27119.399
S2—C17—C22118.57 (14)C27—C26—H27119.403
C18—C17—C22122.3 (2)C26—C27—H28120.233
C17—C18—C19118.1 (3)C28—C27—H28120.236
C18—C19—C20120.4 (2)C23—C28—H29120.572
C19—C20—C21120.1 (3)C27—C28—H29120.574
C20—C21—C22120.9 (3)N3—C29—H30110.938
C17—C22—C21118.17 (19)N3—C29—H31110.938
S2—C23—C24121.85 (15)C30—C29—H30110.950
S2—C23—C28115.46 (18)C30—C29—H31110.951
C24—C23—C28122.58 (19)H30—C29—H31108.967
C23—C24—C25117.3 (3)C29—C30—H32110.984
C24—C25—C26120.5 (3)C29—C30—H33110.979
C25—C26—C27121.2 (3)C31—C30—H32110.982
C26—C27—C28119.5 (3)C31—C30—H33110.986
C23—C28—C27118.9 (3)H32—C30—H33108.994
N3—C29—C30104.0 (2)C30—C31—H34111.013
C29—C30—C31103.9 (2)C30—C31—H35111.012
C30—C31—C32103.70 (19)C32—C31—H34111.020
N3—C32—C31102.7 (3)C32—C31—H35111.031
S1—N2—H19109 (3)H34—C31—H35109.004
S2—N4—H38106 (3)N3—C32—H36111.219
C1—C2—H1121.247N3—C32—H37111.222
C3—C2—H1121.241C31—C32—H36111.218
C2—C3—H2119.661C31—C32—H37111.218
C4—C3—H2119.660H36—C32—H37109.134
N2—S1—N1—C1360.74 (19)S2—N3—C32—C31152.09 (12)
N2—S1—N1—C1674.31 (18)C29—N3—C32—C3115.6 (2)
N1—S1—C1—C237.16 (19)C32—N3—C29—C309.1 (2)
N1—S1—C1—C6146.68 (16)S1—C1—C2—C3175.87 (16)
C1—S1—N1—C1358.94 (14)S1—C1—C6—C5176.40 (17)
C1—S1—N1—C16166.01 (12)C2—C1—C6—C50.4 (4)
N1—S1—C7—C8150.09 (12)C6—C1—C2—C30.1 (4)
N1—S1—C7—C1234.47 (14)C1—C2—C3—C40.6 (5)
C7—S1—N1—C13169.32 (12)C2—C3—C4—C50.6 (5)
C7—S1—N1—C1655.63 (13)C3—C4—C5—C60.2 (6)
N2—S1—C1—C2167.98 (17)C4—C5—C6—C10.3 (5)
N2—S1—C1—C615.9 (2)S1—C7—C8—C9176.01 (12)
N2—S1—C7—C814.98 (16)S1—C7—C12—C11176.09 (11)
N2—S1—C7—C12169.58 (12)C8—C7—C12—C110.9 (3)
C1—S1—C7—C8102.46 (14)C12—C7—C8—C90.6 (3)
C1—S1—C7—C1272.97 (14)C7—C8—C9—C100.3 (3)
C7—S1—C1—C269.15 (19)C8—C9—C10—C110.2 (3)
C7—S1—C1—C6107.00 (16)C9—C10—C11—C120.4 (3)
N4—S2—N3—C2975.95 (17)C10—C11—C12—C70.8 (3)
N4—S2—N3—C3256.79 (17)N1—C13—C14—C1535.6 (3)
N3—S2—C17—C1837.29 (14)C13—C14—C15—C1638.2 (3)
N3—S2—C17—C22146.53 (12)C14—C15—C16—N124.7 (3)
C17—S2—N3—C29164.87 (11)S2—C17—C18—C19176.20 (11)
C17—S2—N3—C3262.38 (13)S2—C17—C22—C21176.26 (10)
N3—S2—C23—C2435.34 (18)C18—C17—C22—C210.2 (3)
N3—S2—C23—C28148.21 (14)C22—C17—C18—C190.2 (3)
C23—S2—N3—C2955.27 (13)C17—C18—C19—C200.3 (3)
C23—S2—N3—C32171.98 (11)C18—C19—C20—C210.8 (3)
N4—S2—C17—C18167.96 (11)C19—C20—C21—C220.8 (3)
N4—S2—C17—C2215.86 (14)C20—C21—C22—C170.3 (3)
N4—S2—C23—C24171.07 (16)S2—C23—C24—C25176.69 (16)
N4—S2—C23—C2812.5 (2)S2—C23—C28—C27176.52 (16)
C17—S2—C23—C2472.31 (18)C24—C23—C28—C270.1 (4)
C17—S2—C23—C28104.14 (15)C28—C23—C24—C250.5 (4)
C23—S2—C17—C1868.86 (14)C23—C24—C25—C260.9 (5)
C23—S2—C17—C22107.32 (13)C24—C25—C26—C271.0 (6)
S1—N1—C13—C14158.92 (12)C25—C26—C27—C280.6 (6)
S1—N1—C16—C15136.13 (13)C26—C27—C28—C230.1 (5)
C13—N1—C16—C152.3 (2)N3—C29—C30—C3130.1 (3)
C16—N1—C13—C1420.6 (2)C29—C30—C31—C3240.5 (3)
S2—N3—C29—C30126.00 (13)C30—C31—C32—N333.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H19···O2i0.76 (4)2.34 (4)3.057 (4)159 (4)
N4—H38···O8ii0.79 (3)2.16 (3)2.952 (4)173 (3)
C2—H1···O10.952.583.531 (3)178
C10—H8···O7iii0.952.563.453 (4)157
C12—H10···O10.952.433.379 (4)174
C16—H18···O4i0.992.583.392 (4)139
C18—H20···O60.952.473.362 (3)156
C25—H26···O3iv0.952.573.512 (5)171
C29—H30···O5ii0.992.503.344 (3)142
C28—H29···N4v0.952.583.401 (4)145
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2; (iv) x, y+1/2, z1/2; (v) x, y, z+1.
 

Acknowledgements

This work was supported in part by a Grant-in-Aid for Scientific Research on Priority Areas from the Ministry of Education, Science, Sports and Culture, Japan (Nos. 09239218 and 14044032) and Japan Society for the Promotion of Science, JSPS (No. P11336). The authors are grateful to the Department of Applied Chemistry, Faculty of Engineering, University of Toyama, for the provision of laboratory facilities. The authors acknowledge the University of Toyama for providing funds for single-crystal X-ray analyses.

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