research communications
Synthesis, spectroscopic and N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(ethylsulfanyl)-1H-pyrazol-5-yl}-2,2,2-trifluoroacetamide
studies ofaDepartment of Chemistry, B.N.M. Institute of Technology, Bengaluru-560 070, India, bHoneychem Pharma Research Pvt. Ltd., Peenya Industrial Area, Bengaluru-560 058, India, cT. John Institute of Technology, Bengaluru-560 083, India, dDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and eDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
*Correspondence e-mail: yathirajan@hotmail.com
The structure of the title compound, C15H8N4Cl2F6OS, a phenylpyrazole-based insecticide related to ethiprole, fipronil, and derivatives thereof is presented. The pyrazole ring has four chemically diverse substituents, namely a nitrogen-bound 2,6-dichloro-4-trifluoromethylphenyl and carbon-bound cyano, ethylsulfanyl, and 2,2,2-trifluoroacetamide groups. The pyrazole and phenyl rings are perpendicular, subtending a dihedral angle of 89.80 (5)°. In the crystal, strong N—H⋯O hydrogen bonds link the molecules into chains that extend parallel to the a-axis.
Keywords: crystal structure; phenylpyrazole; insecticide.
CCDC reference: 2210523
1. Chemical context
The title compound is a phenylpyrazole-based insecticide. It is related to ethiprole, an insecticide used to kill or remove insects from crops and grains during storage (Arthur, 2002). Phenylpyrazole insecticides render an insect's central nervous system toxic by blocking the body's glutamate-gated chloride channel. Ethiprole itself is a non-systemic insecticide that is effective against a wide range of chewing and sucking insects (Wu, 1998) and is an active ingredient used in many insecticides for crop-protection products. Fipronil (see, for example, Park et al., 2017) and fipronil sulfone belong to the same class of compounds. The design, synthesis, and insecticidal activity of novel phenylpyrazoles containing a 2,2,2-trichloro-1-alkoxyethyl moiety have been published by Zhao et al. (2010).
The starting material for the title compound, 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfanyl-1H-pyrazole-3-carbonitrile, is also an important intermediate in the preparation of ethiprole. In view of the importance of phenylpyrazoles, especially in the context of their use in insecticides, this paper reports the synthesis, and spectroscopic studies of the phenylpyrazole derivative, C15H8N4Cl2F6OS (I).
2. Structural commentary
The molecular structure of I (Fig. 1), consists of a pyrazole ring with four chemically diverse substituents. A 2,6-dichloro-4-trifluoromethylphenyl group is attached to atom N1 of the pyrazole ring. A 2,2,2-trifluoroacetamide group is attached to the adjacent carbon of the pyrazole, with ethylsulfanyl and cyano substituents attached sequentially at the next two carbon atoms of the pyrazole. The pyrazole and phenyl rings are essentially perpendicular, forming a dihedral angle of 89.80 (5)°. The mean plane of the amide group (r.m.s. deviation = 0.0079 Å) forms a dihedral angle of 74.33 (6)° with the pyrazole ring, while the dihedral angle between the plane of the ethylsulfanyl substituent and the pyrazole is 81.31 (8)°. There are no unusual bond lengths, bond angles, or torsion angles in the structure, and no noteworthy intramolecular interactions.
3. Supramolecular features
There is only one strong intermolecular hydrogen bond in I, namely N3—H3N⋯O1i (symmetry codes as per Table 1), between c-glide related acetamide groups (Table 1), which propagates to form chains that extend parallel to the a-axis (Fig. 2). The default HTAB command in SHELXL (Sheldrick, 2015b) also flags three C—H⋯F close contacts (Table 1). Two of these, C11—H11⋯F5iii and C13—H13⋯F6iv, are oriented so as to associate 21-screw-related molecules into chains, which again extend parallel to the a-axis (Fig. 3). There are no π–π stacking interactions, but inversion-related molecules have their Cl1 atoms mutually located directly over the benzene rings of their inversion-related counterparts [Cl1⋯Cg(C9–C14)v = 3.4967 (6) Å, where Cg represents the ring centroid], as shown in Table 1 and Fig. 4. These combine to produce pleated sheets that extend in the ac plane (Fig. 5), which then stack along the b-axis direction. Atom–atom contact coverages derived from a Hirshfeld-surface analysis using CrystalExplorer (Spackman et al., 2021) are given in Table 2.
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4. Database survey
A search of the Cambridge Structural Database (CSD version 5.43 with updates through June 2022; Groom et al., 2016) for the 1-phenyl-cyanopyrazole fragment of I gave 82 hits. A search on this fragment with any nitrogen-bound substituent at the equivalent of C1 (i.e., the carbon adjacent to the substituted nitrogen) gave 76 hits, and a subsequent search with 2,6-dichloro-4-(trifluoromethyl)phenyl attached at N1 of the pyrazole ring gave 60 hits. Further addition of any sulfur-bound substituent at the equivalent of C2 gave nine hits, only eight of which are unique. Two of these structures, FOCCUW (Tang, Zhong, Li et al., 2005) and TOLFUY (Du et al., 2019) are dimers. The remaining six, along with three other similar structures, are listed in Table 3.
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5. Synthesis, crystallization and spectroscopic details
Trifluoroacetic anhydride (550 µL, 3.8 mmol) was added dropwise to a stirred solution of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfanyl-1H-pyrazole-3-carbonitrile (a gift from Honeychem Pharma: 724 mg, 1.9 mmol), triethylamine (412 mg, 5.7 mmol) and DCM (5 ml) at 273 K. The reaction was kept at 273 K for 5 h, warmed to room temperature over 3 h, quenched with water and extracted with DCM three times. An overall scheme for the reaction is shown in Fig. 6. The combined organic extracts were washed with water and brine. The crude residue obtained after drying with sodium sulfate followed by concentration, was purified by using ethyl acetate:hexane (2:3) as to give N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(ethylsulfanyl)-1H-pyrazol-5-yl}-2,2,2-trifluoroacetamide (C15H8Cl2F6N4OS, I, yield = 600 mg, 85%).
The product was dissolved in ethanol at 333 K and stirred for 30 min. The resulting solution was allowed to cool slowly to room temperature with slow evaporation. X-ray-quality crystals appeared in two days (m.p. 366–367 K).
The title compound was characterized by IR and 1H NMR spectroscopies, as follows: FT–IR (ν in cm−1): 3227 (N—H stretching), 2250 (C=N stretching), 1737 (C=O stretching), 1694–1652 (C=C stretching), 1313, 1222 (C—F stretching), 881, 818 (s, Ar–C—H bending), 711, 628 (C—Cl). 1H NMR: DMSO–d6 (400 MHz, δ ppm): 12.42 (b, 1H, NH), 8.36 (s, 2H, Ar—H), 2.90–2.85 (q, 2H, CH2, J = 7.6 Hz), 1.19–1.15 (t, 3H, CH3, J = 7.6 Hz).
6. Refinement
Crystal data, data collection, and structure . All H atoms were found in difference-Fourier maps. Carbon-bound hydrogens were subsequently included in the using riding models, with constrained distances set to 0.98 Å (RCH3), 0.99 Å (R2CH2) and 0.95 Å (R2CH). The nitrogen-bound hydrogen-atom coordinates were refined freely. Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq (RCH3 only) of the attached atom.
details are summarized in Table 4
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Supporting information
CCDC reference: 2210523
https://doi.org/10.1107/S2056989022009653/tx2059sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009653/tx2059Isup2.hkl
Data collection: APEX3 (Bruker, 2016); cell
APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELX (Sheldrick, 2008) and publCIF (Westrip, 2010).C15H8Cl2F6N4OS | Dx = 1.697 Mg m−3 |
Mr = 477.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9972 reflections |
a = 9.9350 (3) Å | θ = 2.5–27.5° |
b = 17.5133 (7) Å | µ = 0.53 mm−1 |
c = 21.4662 (8) Å | T = 90 K |
V = 3735.0 (2) Å3 | Cut block, colourless |
Z = 8 | 0.30 × 0.23 × 0.19 mm |
F(000) = 1904 |
Bruker D8 Venture dual source diffractometer | 4271 independent reflections |
Radiation source: microsource | 3893 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.036 |
φ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −12→10 |
Tmin = 0.831, Tmax = 0.958 | k = −22→22 |
27352 measured reflections | l = −27→27 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0273P)2 + 2.0142P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
4271 reflections | Δρmax = 0.42 e Å−3 |
267 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL-2019/2 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (3) |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.63935 (3) | 0.51208 (2) | 0.40861 (2) | 0.01864 (8) | |
Cl2 | 0.09945 (3) | 0.53537 (2) | 0.40975 (2) | 0.02419 (9) | |
S1 | 0.32287 (3) | 0.38515 (2) | 0.20184 (2) | 0.01658 (8) | |
F1 | 0.35596 (9) | 0.62440 (5) | 0.15112 (4) | 0.02447 (19) | |
F2 | 0.38608 (8) | 0.69639 (4) | 0.23078 (4) | 0.02336 (18) | |
F3 | 0.18898 (8) | 0.68747 (5) | 0.18872 (4) | 0.02659 (19) | |
F4 | 0.36645 (9) | 0.70022 (5) | 0.59601 (4) | 0.02648 (19) | |
F5 | 0.30334 (10) | 0.77508 (5) | 0.52258 (4) | 0.0323 (2) | |
F6 | 0.51380 (8) | 0.75448 (5) | 0.53817 (4) | 0.02669 (19) | |
O1 | 0.15013 (9) | 0.55566 (5) | 0.24758 (4) | 0.01724 (19) | |
N1 | 0.36297 (11) | 0.47239 (6) | 0.36809 (5) | 0.0145 (2) | |
N2 | 0.35250 (11) | 0.39898 (6) | 0.38684 (5) | 0.0168 (2) | |
N3 | 0.37119 (10) | 0.55065 (6) | 0.27566 (5) | 0.0130 (2) | |
H3N | 0.4502 (17) | 0.5686 (8) | 0.2699 (7) | 0.016* | |
N4 | 0.30803 (13) | 0.21428 (6) | 0.33539 (6) | 0.0255 (3) | |
C1 | 0.36015 (12) | 0.47954 (7) | 0.30511 (6) | 0.0131 (2) | |
C2 | 0.34539 (12) | 0.40781 (7) | 0.28031 (6) | 0.0141 (2) | |
C3 | 0.34127 (13) | 0.36032 (7) | 0.33357 (6) | 0.0155 (2) | |
C4 | 0.32423 (14) | 0.27879 (7) | 0.33502 (6) | 0.0185 (3) | |
C5 | 0.49124 (14) | 0.35383 (9) | 0.18065 (6) | 0.0234 (3) | |
H5A | 0.556533 | 0.395746 | 0.187298 | 0.028* | |
H5B | 0.518388 | 0.309910 | 0.206827 | 0.028* | |
C6 | 0.48964 (15) | 0.33069 (9) | 0.11230 (7) | 0.0275 (3) | |
H6A | 0.460330 | 0.374098 | 0.086883 | 0.041* | |
H6B | 0.427263 | 0.287945 | 0.106458 | 0.041* | |
H6C | 0.580318 | 0.315148 | 0.099566 | 0.041* | |
C7 | 0.26356 (12) | 0.58029 (6) | 0.24545 (5) | 0.0131 (2) | |
C8 | 0.29906 (13) | 0.64906 (7) | 0.20371 (6) | 0.0166 (3) | |
C9 | 0.37120 (13) | 0.53275 (7) | 0.41254 (6) | 0.0141 (2) | |
C10 | 0.49581 (12) | 0.55813 (7) | 0.43330 (6) | 0.0140 (2) | |
C11 | 0.50542 (12) | 0.61972 (7) | 0.47388 (5) | 0.0145 (2) | |
H11 | 0.590543 | 0.637395 | 0.487965 | 0.017* | |
C12 | 0.38740 (13) | 0.65467 (7) | 0.49325 (6) | 0.0143 (2) | |
C13 | 0.26172 (13) | 0.62922 (7) | 0.47417 (6) | 0.0160 (2) | |
H13 | 0.182136 | 0.653612 | 0.488522 | 0.019* | |
C14 | 0.25432 (13) | 0.56765 (7) | 0.43387 (6) | 0.0156 (2) | |
C15 | 0.39317 (13) | 0.72121 (7) | 0.53760 (6) | 0.0176 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.01593 (15) | 0.01905 (15) | 0.02095 (16) | 0.00316 (11) | 0.00349 (11) | −0.00045 (11) |
Cl2 | 0.01509 (16) | 0.02479 (17) | 0.03269 (19) | −0.00092 (12) | −0.00540 (13) | −0.00730 (13) |
S1 | 0.01774 (16) | 0.01755 (15) | 0.01445 (15) | 0.00235 (11) | −0.00419 (12) | −0.00360 (11) |
F1 | 0.0328 (5) | 0.0231 (4) | 0.0175 (4) | −0.0014 (3) | 0.0079 (3) | −0.0003 (3) |
F2 | 0.0286 (4) | 0.0160 (4) | 0.0255 (4) | −0.0086 (3) | −0.0006 (3) | −0.0001 (3) |
F3 | 0.0246 (4) | 0.0215 (4) | 0.0336 (5) | 0.0074 (3) | −0.0018 (4) | 0.0101 (3) |
F4 | 0.0389 (5) | 0.0253 (4) | 0.0152 (4) | −0.0056 (4) | 0.0072 (3) | −0.0047 (3) |
F5 | 0.0409 (5) | 0.0182 (4) | 0.0378 (5) | 0.0121 (4) | −0.0129 (4) | −0.0102 (4) |
F6 | 0.0286 (4) | 0.0231 (4) | 0.0285 (4) | −0.0110 (3) | 0.0052 (4) | −0.0093 (3) |
O1 | 0.0122 (4) | 0.0175 (4) | 0.0220 (5) | −0.0002 (3) | −0.0008 (4) | 0.0010 (4) |
N1 | 0.0183 (5) | 0.0108 (5) | 0.0143 (5) | 0.0006 (4) | −0.0015 (4) | −0.0007 (4) |
N2 | 0.0213 (5) | 0.0118 (5) | 0.0172 (5) | 0.0005 (4) | −0.0025 (4) | 0.0006 (4) |
N3 | 0.0104 (5) | 0.0123 (5) | 0.0162 (5) | −0.0011 (4) | −0.0003 (4) | 0.0007 (4) |
N4 | 0.0355 (7) | 0.0170 (5) | 0.0239 (6) | −0.0005 (5) | −0.0053 (5) | 0.0002 (4) |
C1 | 0.0109 (5) | 0.0138 (5) | 0.0146 (6) | 0.0012 (4) | −0.0017 (4) | −0.0001 (4) |
C2 | 0.0131 (5) | 0.0145 (6) | 0.0147 (6) | 0.0012 (4) | −0.0017 (5) | −0.0018 (4) |
C3 | 0.0164 (6) | 0.0132 (5) | 0.0168 (6) | 0.0008 (5) | −0.0026 (5) | −0.0006 (4) |
C4 | 0.0230 (7) | 0.0172 (6) | 0.0153 (6) | 0.0009 (5) | −0.0040 (5) | −0.0005 (5) |
C5 | 0.0188 (6) | 0.0332 (7) | 0.0181 (6) | 0.0040 (6) | 0.0001 (5) | −0.0035 (5) |
C6 | 0.0248 (7) | 0.0388 (8) | 0.0190 (7) | −0.0018 (6) | 0.0022 (6) | −0.0067 (6) |
C7 | 0.0145 (5) | 0.0116 (5) | 0.0132 (5) | 0.0018 (4) | 0.0006 (5) | −0.0026 (4) |
C8 | 0.0180 (6) | 0.0142 (6) | 0.0177 (6) | 0.0007 (5) | −0.0001 (5) | −0.0002 (5) |
C9 | 0.0200 (6) | 0.0110 (5) | 0.0115 (6) | −0.0001 (4) | −0.0017 (5) | 0.0004 (4) |
C10 | 0.0150 (6) | 0.0139 (5) | 0.0131 (6) | 0.0013 (4) | 0.0014 (5) | 0.0024 (4) |
C11 | 0.0161 (6) | 0.0144 (5) | 0.0132 (6) | −0.0024 (4) | −0.0014 (5) | 0.0016 (4) |
C12 | 0.0195 (6) | 0.0114 (5) | 0.0120 (5) | 0.0000 (4) | −0.0002 (5) | 0.0013 (4) |
C13 | 0.0169 (6) | 0.0144 (5) | 0.0166 (6) | 0.0029 (5) | 0.0003 (5) | 0.0003 (4) |
C14 | 0.0151 (6) | 0.0150 (5) | 0.0166 (6) | −0.0003 (5) | −0.0027 (5) | 0.0014 (5) |
C15 | 0.0209 (6) | 0.0146 (6) | 0.0173 (6) | −0.0005 (5) | 0.0000 (5) | −0.0012 (5) |
Cl1—C10 | 1.7219 (12) | C1—C2 | 1.3722 (16) |
Cl2—C14 | 1.7191 (13) | C2—C3 | 1.4143 (17) |
S1—C2 | 1.7450 (13) | C3—C4 | 1.4381 (17) |
S1—C5 | 1.8181 (14) | C5—C6 | 1.5222 (19) |
F1—C8 | 1.3342 (15) | C5—H5A | 0.9900 |
F2—C8 | 1.3312 (15) | C5—H5B | 0.9900 |
F3—C8 | 1.3237 (15) | C6—H6A | 0.9800 |
F4—C15 | 1.3333 (15) | C6—H6B | 0.9800 |
F5—C15 | 1.3381 (15) | C6—H6C | 0.9800 |
F6—C15 | 1.3327 (15) | C7—C8 | 1.5421 (16) |
O1—C7 | 1.2075 (15) | C9—C10 | 1.3888 (17) |
N1—N2 | 1.3511 (14) | C9—C14 | 1.3898 (17) |
N1—C1 | 1.3581 (16) | C10—C11 | 1.3898 (17) |
N1—C9 | 1.4264 (15) | C11—C12 | 1.3865 (17) |
N2—C3 | 1.3337 (16) | C11—H11 | 0.9500 |
N3—C7 | 1.3540 (16) | C12—C13 | 1.3877 (18) |
N3—C1 | 1.4010 (15) | C12—C15 | 1.5059 (17) |
N3—H3N | 0.855 (16) | C13—C14 | 1.3843 (17) |
N4—C4 | 1.1412 (17) | C13—H13 | 0.9500 |
C2—S1—C5 | 101.08 (6) | N3—C7—C8 | 113.4 (1) |
N2—N1—C1 | 112.5 (1) | F3—C8—F2 | 109.04 (10) |
N2—N1—C9 | 120.69 (10) | F3—C8—F1 | 108.0 (1) |
C1—N1—C9 | 126.78 (10) | F2—C8—F1 | 107.2 (1) |
C3—N2—N1 | 103.54 (10) | F3—C8—C7 | 110.44 (10) |
C7—N3—C1 | 119.68 (10) | F2—C8—C7 | 112.41 (10) |
C7—N3—H3N | 121 (1) | F1—C8—C7 | 109.61 (10) |
C1—N3—H3N | 117.7 (10) | C10—C9—C14 | 119.89 (11) |
N1—C1—C2 | 107.7 (1) | C10—C9—N1 | 120.19 (11) |
N1—C1—N3 | 121.98 (10) | C14—C9—N1 | 119.90 (11) |
C2—C1—N3 | 130.32 (12) | C9—C10—C11 | 120.71 (11) |
C1—C2—C3 | 103.17 (11) | C9—C10—Cl1 | 119.31 (9) |
C1—C2—S1 | 126.61 (10) | C11—C10—Cl1 | 119.97 (10) |
C3—C2—S1 | 130.01 (9) | C12—C11—C10 | 118.20 (11) |
N2—C3—C2 | 113.09 (11) | C12—C11—H11 | 120.9 |
N2—C3—C4 | 119.69 (11) | C10—C11—H11 | 120.9 |
C2—C3—C4 | 127.21 (11) | C11—C12—C13 | 122.05 (11) |
N4—C4—C3 | 178.42 (15) | C11—C12—C15 | 119.94 (11) |
C6—C5—S1 | 108.17 (10) | C13—C12—C15 | 118.00 (11) |
C6—C5—H5A | 110.1 | C14—C13—C12 | 118.84 (12) |
S1—C5—H5A | 110.1 | C14—C13—H13 | 120.6 |
C6—C5—H5B | 110.1 | C12—C13—H13 | 120.6 |
S1—C5—H5B | 110.1 | C13—C14—C9 | 120.27 (12) |
H5A—C5—H5B | 108.4 | C13—C14—Cl2 | 119.47 (10) |
C5—C6—H6A | 109.5 | C9—C14—Cl2 | 120.26 (9) |
C5—C6—H6B | 109.5 | F6—C15—F4 | 106.92 (11) |
H6A—C6—H6B | 109.5 | F6—C15—F5 | 107.08 (10) |
C5—C6—H6C | 109.5 | F4—C15—F5 | 106.75 (11) |
H6A—C6—H6C | 109.5 | F6—C15—C12 | 112.23 (11) |
H6B—C6—H6C | 109.5 | F4—C15—C12 | 111.94 (10) |
O1—C7—N3 | 125.59 (11) | F5—C15—C12 | 111.58 (11) |
O1—C7—C8 | 120.96 (11) | ||
C1—N1—N2—C3 | −0.77 (14) | N3—C7—C8—F1 | 77.52 (13) |
C9—N1—N2—C3 | 177.32 (11) | N2—N1—C9—C10 | 91.61 (15) |
N2—N1—C1—C2 | 0.79 (14) | C1—N1—C9—C10 | −90.59 (15) |
C9—N1—C1—C2 | −177.16 (11) | N2—N1—C9—C14 | −90.12 (14) |
N2—N1—C1—N3 | −179.23 (11) | C1—N1—C9—C14 | 87.67 (16) |
C9—N1—C1—N3 | 2.82 (19) | C14—C9—C10—C11 | −1.93 (18) |
C7—N3—C1—N1 | −111.17 (13) | N1—C9—C10—C11 | 176.34 (11) |
C7—N3—C1—C2 | 68.80 (18) | C14—C9—C10—Cl1 | 177.67 (9) |
N1—C1—C2—C3 | −0.45 (13) | N1—C9—C10—Cl1 | −4.06 (16) |
N3—C1—C2—C3 | 179.58 (12) | C9—C10—C11—C12 | 0.37 (18) |
N1—C1—C2—S1 | 174.65 (9) | Cl1—C10—C11—C12 | −179.23 (9) |
N3—C1—C2—S1 | −5.3 (2) | C10—C11—C12—C13 | 1.06 (18) |
C5—S1—C2—C1 | 101.74 (12) | C10—C11—C12—C15 | 179.53 (11) |
C5—S1—C2—C3 | −84.50 (13) | C11—C12—C13—C14 | −0.90 (18) |
N1—N2—C3—C2 | 0.47 (14) | C15—C12—C13—C14 | −179.39 (11) |
N1—N2—C3—C4 | −178.34 (12) | C12—C13—C14—C9 | −0.69 (18) |
C1—C2—C3—N2 | −0.02 (14) | C12—C13—C14—Cl2 | −179.99 (9) |
S1—C2—C3—N2 | −174.87 (10) | C10—C9—C14—C13 | 2.09 (18) |
C1—C2—C3—C4 | 178.68 (13) | N1—C9—C14—C13 | −176.18 (11) |
S1—C2—C3—C4 | 3.8 (2) | C10—C9—C14—Cl2 | −178.62 (9) |
C2—S1—C5—C6 | 179.48 (10) | N1—C9—C14—Cl2 | 3.11 (16) |
C1—N3—C7—O1 | 10.00 (18) | C11—C12—C15—F6 | 20.04 (16) |
C1—N3—C7—C8 | −167.28 (10) | C13—C12—C15—F6 | −161.43 (11) |
O1—C7—C8—F3 | 18.96 (16) | C11—C12—C15—F4 | −100.19 (13) |
N3—C7—C8—F3 | −163.61 (10) | C13—C12—C15—F4 | 78.33 (14) |
O1—C7—C8—F2 | 140.97 (12) | C11—C12—C15—F5 | 140.24 (12) |
N3—C7—C8—F2 | −41.60 (14) | C13—C12—C15—F5 | −41.23 (16) |
O1—C7—C8—F1 | −99.91 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O1i | 0.855 (16) | 2.034 (16) | 2.8172 (13) | 151.9 (14) |
C5—H5B···F2ii | 0.99 | 2.58 | 3.5641 (16) | 174 |
C11—H11···F5iii | 0.95 | 2.62 | 3.4873 (15) | 152 |
C13—H13···F6iv | 0.95 | 2.39 | 3.2071 (15) | 144 |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+3/2, −z+1. |
Cg(C9–C14) represents the centroid of C9–C14 benzene ring. |
Atoms | D—H | H···A | D···A | D—H···A |
N3—H3N···O1i | 0.855 (16) | 2.034 (16) | 2.8172 (13) | 151.9 (14) |
C5—H5B···F2ii | 0.99 | 2.58 | 3.5641 (16) | 173.9 |
C11—H11···F5iii | 0.95 | 2.62 | 3.4873 (15) | 151.8 |
C13—H13···F6iv | 0.95 | 2.39 | 3.2071 (15) | 143.8 |
Cl1···Cg(C9–C14)v | 3.4967 (6) |
Symmetry codes: (i) x + 1/2, y, -z + 1/2; (ii) -x + 1, y - 1/2, -z + 1/2; (iii) x + 1/2, -y + 3/2, -z + 1; (iv) x - 1/2, -y + 3/2, -z + 1; (v) -x + 1, -y + 1, -z + 1. |
Atom contacts | % | Atom contacts | % |
H···F/F···H | 23.0 | F···Cl/Cl···F | 8.3 |
N···F/F···N | 7.3 | C···H/H···C | 7.1 |
H···Cl/Cl···H | 7.1 | H···N/N···H | 6.9 |
H···O/O···H | 5.9 | H···H | 4.8 |
C···F/F···C | 3.8 | C···Cl/Cl···C | 3.8 |
C···N/N···C | 3.4 | F···S/S···F | 3.0 |
S···Cl/Cl···S | 1.9 | Cl···Cl | 1.3 |
H···S/S···H | 1.3 | O···Cl/Cl···O | 1.2 |
C···C | 0.9 | O···N/N···O | 0.8 |
N···Cl/Cl···N | 0.7 | N···N | 0.3 |
O···F/F···O | 0.2 | C···S/S···C | 0.2 |
C···O/O···C | 0.1 |
All other atom–atom contact coverages are ~0.0 % |
All entries have 2,6-dichloro-4-(trifluoromethyl)phenyl and cyano groups attached at the equivalent of N1 and C3 of I, respectively. Substituents R' and R¨ represent groups attached at the equivalent of C1 and C2 in I, respectively. |
CSD code | R' | R" | Reference |
DUKVAJ | NHCOCH2Ph | SOCF3 | Chen et al. (2020) |
EFIXEZ | NHCOCHCHPh | SOCF3 | Chen (2019) |
PAZFAY | NH2 | SCF3 | Tang, Zhong, Lin et al. (2005) |
TOLFAE | NHCH2PhOMe | SOCF3 | Chen & Wu (2019) |
YEGJAY | NH2 | SOCF3 | Park et al. (2017) |
ZITNAU | NHCHPhF | SOCF3 | Chen et al. (2019) |
GIXDAT | NH2 | I | Li et al. (2007) |
HILTUS | NH2 | H | Luo et al. (2007) |
TIDNUP | NH2 | CF3 | Hainzl & Casida (1996) |
Acknowledgements
PP is grateful to the B. N. M. Institute of Technology for research facilities.
Funding information
HSY is grateful to UGC, New Delhi, for the award of BSR Faculty Fellowship for three years. Funding for this research was provided by: NSF (MRI CHE1625732) and the University of Kentucky (Bruker D8 Venture diffractometer).
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