research communications
Crystal structures of three substituted 3-aryl-2-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-ones
aDepartment of Chemistry, Pennsylvania State University, University Park, PA 16802, USA, and bPennsylvania State University, Schuylkill Campus, 200 University Drive, Schuylkill Haven, PA 17972, USA
*Correspondence e-mail: ljs43@psu.edu
Three ring-substituted 3-aryl analogs of 2-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one, namely 3-(4-methoxyphenyl)-2-phenyl-4H-1,3-benzothiazin-4-one, C21H17NO2S, (I), 2-phenyl-3-[4-(trifluoromethyl)phenyl]-2,3-dihydro-4H-1,3-benzothiazin-4-one toluene hemisolvate, C21H14F3NOS·0.5C7H8, (II), and 3-(3-bromophenyl)-2-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one toluene hemisolvate, C20H14BrNOS·0.5C7H8, (III), were synthesized and their crystal structures determined. The hemisolvates differ in that in (II), the comprises two molecules of the benzothiazinone compound and a toluene solvent molecule, whereas in (III), the unit comprises one benzothiazinone molecule and a half-occupancy toluene solvent molecule. All crystals are of racemic mixtures of the chiral 2-C atom of the thiazine moiety, which in all structures has a screw-boat puckering, with the puckering amplitude values within the range 0.575–0.603 Å. In all three structures, the benzene plane of the benzothiazine system makes a dihedral angle in the range 78.60 (5) to 98.40 (5)° with the unsubstituted benzene plane and in the range 70.50 (1) to 121.00 (5)° with the substituted benzene plane. The CF3 substituent group in one of the molecules of (II) shows positional disorder, with an occupancy ratio of 0.57 (3):0.43 (3). In the crystals of (I) and (II), weak intermolecular C—H⋯O interactions are present, giving in (I), molecules arranged in a plane parallel to (010), and in (II), chains along a. In addition, all three structures show weak C—H⋯π interactions involving various aromatic rings.
1. Chemical context
We have previously reported the crystal structures of 2,3-diphenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one (Yennawar et al., 2014) and three 2-aryl-3-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-ones (Yennawar et al., 2013, 2015). In the present communication, we report the synthesis and crystal structures of three ring-substituted 3-aryl-2-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-ones, namely the 4-methoxyphenyl compound, (I), the 4-(trifluoromethyl)phenyl compound as the toluene hemisolvate, (II), and the 4-bromophenyl compound as the toluene hemisolvate, (III). However, (II) and (III) differ in that the of (II) comprises two independent benzothiazinone molecules and one toluene solvent molecule, while that of (III) comprises one benzothiazinone molecule and a half-occupancy toluene solvent molecule. Each compound has been synthesized using the same T3P/pyridine (T3P is 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane 2,4,6-trioxide) method that was used for the preparation of the previously mentioned analogous compounds (Yennawar et al., 2013, 2014, 2015).
2. Structural commentary
The three benzothiazinones (Figs. 1–3) exhibit fairly similar conformations. In all three, the thiazine ring pucker is screw-boat, with θ between 63.0 and 67.1°, and puckering amplitudes within the range 0.575–0.603 Å. The interplanar angle between the benzene ring of the benzothiazine system and the substituent benzene rings at the 2-position are 82.68 (6)° in (I), 95.69 (5) and 78.10 (5)° in (II), and 98.37 (1)° in (III). Those with the benzene rings at the 3-position are 59.10 (6)° in (I), 70.56 (5) and 72.26 (5)° in (II), and 78.66 (1)° in (III). The CF3 substituent group in one of the molecules of (II) shows positional disorder, with an occupancy ratio of 0.57 (3):0.43 (3).
3. Supramolecular features
In (I) and (II), weak intermolecular C—H⋯O interactions are observed (Tables 1 and 2, respectively), giving in (I), molecules arranged in a plane parallel to (010) (Fig. 4), and in (II), chains along the a-axis direction (Fig. 5). The crystals also feature T-type C—H⋯π interactions (Tables 1–3), as analyzed using PLATON (Spek, 2009). In (I), a weak C—H⋯Cg(π ring) interaction of 3.8068 (10) Å is present with an interacting angle of 148°. In (II), the toluene molecule participates in tilted-T-type interactions by placing itself obliquely between phenyl rings of the two enantiomers, with C—H⋯Cg(toluene) distances of 3.5916 (7) and 3.6009 (7) Å, with interacting angles of 145 and 147°, respectively. In (III), two C—H⋯π interactions, one between the thiazine ring and the toluene solvent molecule and the other between the fused benzene ring and the 2-phenyl ring, have C—H⋯Cg distances of 3.5802 (6) and 3.6823 (6) Å, with interacting angles of 156 and 153°, respectively (Fig. 6). Structure (I) also shows a very weak parallel-displaced π–π interaction between symmetry-related benzene rings, with an inter-centroid (Cg⋯Cg) distance of 3.977 (1) Å and an interplanar angle of 8°.
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4. Database survey
The three structures reported here and four previously reported analogous structures (Yennawar et al., 2013, 2014, 2015) have very similar screw-boat puckering for the thiazine ring. Among the seven crystal structures, the variation in the interplanar angles between the benzene ring of the benzothiazine moiety and the two substituent benzene rings at positions 2 and 3 lie within 26 and 30°, respectively. A structure for 2-(5-methylthiophen-2-yl)-3-phenyl-2,3-dihydroquinazolin-4(1H)-one has been reported in a patent application (Atwood et al., 2015).
5. Synthesis and crystallization
A two-necked 25 ml round-bottomed flask was oven-dried, cooled under N2 and charged with a stir bar and an N-aryl-C-phenylimine (6 mmol). Tetrahydrofuran or 2-methyltetrahydrofuran (2.3 ml) was added, the solid dissolved and the solution stirred. Pyridine (1.95 ml, 24 mmol) was added, followed by thiosalicylic acid (0.93 g, 6 mmol). Finally, 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane 2,4,6-trioxide (T3P) in 2-methyltetrahydrofuran (50 wt%, 7.3 ml, 12 mmol) was added. The mixture was stirred at room temperature and the reaction was followed using The mixture was then poured into a separatory funnel and dichloromethane and distilled water were added. The layers were separated and the aqueous layer was then extracted twice with dichloromethane. The organics were combined and washed with saturated sodium bicarbonate and then saturated sodium chloride. The organic extract was dried over sodium sulfate and concentrated under vacuum. The crude product was chromatographed on 30 g of flash silica gel using mixtures of ethyl acetate and hexanes, and then further purified as indicated below.
Compound (I) was recrystallized from ethanol solution to give yellow crystals (yield 0.72 g, 34.6%; m.p. 365–369 K). RF = 0.52 (50% ethyl acetate/hexanes). Colorless block-shaped crystals suitable for the X-ray analysis were grown by slow evaporation from ethanol solution.
Compound (II) was recrystallized from methylene chloride/hexanes to give yellow crystals (yield 0.5639 g, 24.4%; m.p. 404–406 K). RF = 0.56 (30% ethyl acetate/hexanes solution). Colorless needle-shaped crystals suitable for the X-ray analysis were grown by slow evaporation from toluene solution.
Compound (III) was triturated with hexanes solution to give a solid (0.7242 g) and then recrystallized from toluene/hexanes to give white crystals (yield 0.3544 g, 14.5%; m.p.: 358–359 K). RF = 0.39 (20% ethyl acetate/hexanes). A second crop of 0.30 g (12.7%) was obtained by slow evaporation of the mother liquor, giving colorless blocks suitable for the X-ray analysis.
6. Refinement
Crystal data, data collection and structure . In the of (II), the two molecules in the were restrained using the SAME command in SHELXL2014 (Sheldrick, 2015). One of the molecules shows positional disorder in the –CF3 group, with the occupancy ratio refining to 0.57 (3):0.43 (3). We tried to address the high R values (relative to Rint) by looking for and using restraints but we have had no success in achieving respectable R values. In (III), the disordered partial toluene molecule was refined with a site-occupancy factor determined as 0.50 and with positional constraints (AFIX 6). In all three compounds, the H atoms were placed geometrically and allowed to ride on the C atoms during with C—H distances of 0.98 (methine), 0.96 (methyl) or 0.93 Å (aromatic) and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise.
details are summarized in Table 4
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Supporting information
https://doi.org/10.1107/S2056989016011002/zs2362sup1.cif
contains datablocks 1, II, III, I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989016011002/zs2362Isup2.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989016011002/zs2362IIsup3.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989016011002/zs2362IIIsup4.cml
For all compounds, data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for (I); SHELXL97 (Sheldrick, 2008) for (II); SHELXL014 (Sheldrick, 2015) for (III). For all compounds, molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C21H17NO2S | F(000) = 1456 |
Mr = 347.42 | Dx = 1.328 Mg m−3 |
Monoclinic, C2/c | Melting point = 365–369 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 17.820 (4) Å | Cell parameters from 4847 reflections |
b = 11.016 (3) Å | θ = 2.3–28.3° |
c = 17.890 (4) Å | µ = 0.20 mm−1 |
β = 98.385 (5)° | T = 298 K |
V = 3474.4 (15) Å3 | Block, colorless |
Z = 8 | 0.26 × 0.24 × 0.12 mm |
Bruker CCD area-detector diffractometer | 4284 independent reflections |
Radiation source: fine-focus sealed tube | 3414 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
phi and ω scans | θmax = 28.3°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −20→23 |
Tmin = 0.940, Tmax = 0.986 | k = −14→14 |
15005 measured reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0702P)2 + 0.7957P] where P = (Fo2 + 2Fc2)/3 |
4284 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Experimental. Absorption correction: SADABS (Bruker, 2001) was used for absorption correction. R(int) was 0.0415 before and 0.0233 after correction. The λ/2 correction factor is 0.0015. |
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. |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.17986 (7) | 0.37162 (13) | 0.33545 (8) | 0.0429 (3) | |
H1 | 0.1812 | 0.3332 | 0.3850 | 0.052* | |
C2 | 0.28205 (7) | 0.42680 (12) | 0.26124 (7) | 0.0387 (3) | |
C3 | 0.22572 (8) | 0.41320 (12) | 0.19132 (8) | 0.0411 (3) | |
C4 | 0.16382 (8) | 0.33411 (13) | 0.18637 (8) | 0.0453 (3) | |
C5 | 0.11974 (9) | 0.31295 (16) | 0.11634 (10) | 0.0604 (4) | |
H5 | 0.0793 | 0.2588 | 0.1126 | 0.072* | |
C6 | 0.13587 (11) | 0.3717 (2) | 0.05331 (10) | 0.0709 (5) | |
H6 | 0.1068 | 0.3565 | 0.0068 | 0.085* | |
C7 | 0.19525 (11) | 0.4538 (2) | 0.05825 (10) | 0.0689 (5) | |
H7 | 0.2047 | 0.4957 | 0.0155 | 0.083* | |
C8 | 0.24026 (9) | 0.47316 (15) | 0.12662 (8) | 0.0529 (4) | |
H8 | 0.2808 | 0.5270 | 0.1295 | 0.063* | |
C9 | 0.12871 (7) | 0.48211 (12) | 0.33619 (7) | 0.0395 (3) | |
C10 | 0.15308 (9) | 0.59940 (14) | 0.32618 (9) | 0.0491 (3) | |
H10 | 0.2023 | 0.6131 | 0.3168 | 0.059* | |
C11 | 0.10443 (10) | 0.69663 (15) | 0.33011 (10) | 0.0571 (4) | |
H11 | 0.1213 | 0.7752 | 0.3232 | 0.068* | |
C12 | 0.03146 (10) | 0.67779 (16) | 0.34414 (10) | 0.0578 (4) | |
H12 | −0.0010 | 0.7433 | 0.3469 | 0.069* | |
C13 | 0.00683 (9) | 0.56148 (16) | 0.35406 (10) | 0.0562 (4) | |
H13 | −0.0425 | 0.5484 | 0.3635 | 0.067* | |
C14 | 0.05456 (8) | 0.46423 (15) | 0.35005 (8) | 0.0484 (3) | |
H14 | 0.0372 | 0.3859 | 0.3567 | 0.058* | |
C15 | 0.31352 (7) | 0.39619 (13) | 0.39612 (7) | 0.0405 (3) | |
C16 | 0.34533 (10) | 0.28627 (14) | 0.42046 (9) | 0.0530 (4) | |
H16 | 0.3329 | 0.2165 | 0.3921 | 0.064* | |
C17 | 0.39550 (10) | 0.27956 (15) | 0.48685 (9) | 0.0568 (4) | |
H17 | 0.4167 | 0.2053 | 0.5031 | 0.068* | |
C18 | 0.41438 (8) | 0.38303 (14) | 0.52936 (7) | 0.0441 (3) | |
C19 | 0.38413 (9) | 0.49301 (14) | 0.50441 (9) | 0.0499 (4) | |
H19 | 0.3975 | 0.5632 | 0.5320 | 0.060* | |
C20 | 0.33346 (8) | 0.49867 (13) | 0.43761 (9) | 0.0492 (4) | |
H20 | 0.3128 | 0.5731 | 0.4209 | 0.059* | |
C21 | 0.48531 (10) | 0.46879 (18) | 0.64109 (9) | 0.0625 (5) | |
H21A | 0.5066 | 0.5295 | 0.6119 | 0.094* | |
H21B | 0.5224 | 0.4448 | 0.6829 | 0.094* | |
H21C | 0.4416 | 0.5014 | 0.6598 | 0.094* | |
N1 | 0.25868 (6) | 0.39985 (11) | 0.32831 (6) | 0.0424 (3) | |
O1 | 0.34743 (5) | 0.45779 (10) | 0.25787 (6) | 0.0511 (3) | |
O2 | 0.46342 (7) | 0.36572 (11) | 0.59465 (6) | 0.0601 (3) | |
S1 | 0.14215 (2) | 0.25763 (3) | 0.26647 (3) | 0.05493 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0365 (7) | 0.0455 (7) | 0.0465 (7) | −0.0048 (6) | 0.0049 (6) | 0.0087 (6) |
C2 | 0.0370 (7) | 0.0353 (6) | 0.0438 (7) | 0.0003 (5) | 0.0057 (5) | −0.0008 (5) |
C3 | 0.0392 (7) | 0.0404 (7) | 0.0431 (7) | 0.0045 (6) | 0.0043 (5) | −0.0041 (5) |
C4 | 0.0393 (7) | 0.0398 (7) | 0.0558 (8) | 0.0048 (6) | 0.0040 (6) | −0.0100 (6) |
C5 | 0.0439 (8) | 0.0628 (10) | 0.0712 (11) | 0.0028 (8) | −0.0025 (7) | −0.0260 (9) |
C6 | 0.0614 (11) | 0.0961 (15) | 0.0507 (9) | 0.0139 (10) | −0.0065 (8) | −0.0204 (9) |
C7 | 0.0690 (12) | 0.0926 (14) | 0.0445 (8) | 0.0150 (11) | 0.0065 (8) | 0.0023 (9) |
C8 | 0.0531 (9) | 0.0593 (9) | 0.0465 (8) | 0.0037 (7) | 0.0083 (7) | 0.0012 (7) |
C9 | 0.0349 (6) | 0.0451 (7) | 0.0379 (6) | −0.0037 (6) | 0.0031 (5) | 0.0028 (5) |
C10 | 0.0403 (7) | 0.0490 (8) | 0.0594 (8) | −0.0051 (6) | 0.0116 (6) | 0.0050 (7) |
C11 | 0.0588 (10) | 0.0440 (8) | 0.0702 (10) | −0.0028 (7) | 0.0151 (8) | 0.0016 (7) |
C12 | 0.0535 (9) | 0.0549 (9) | 0.0662 (10) | 0.0077 (8) | 0.0126 (8) | −0.0030 (8) |
C13 | 0.0381 (8) | 0.0645 (10) | 0.0678 (10) | −0.0003 (7) | 0.0135 (7) | 0.0004 (8) |
C14 | 0.0399 (7) | 0.0506 (8) | 0.0556 (8) | −0.0065 (6) | 0.0097 (6) | 0.0043 (6) |
C15 | 0.0350 (7) | 0.0462 (7) | 0.0398 (6) | 0.0015 (6) | 0.0040 (5) | 0.0035 (5) |
C16 | 0.0606 (10) | 0.0422 (8) | 0.0521 (8) | 0.0055 (7) | −0.0059 (7) | −0.0043 (6) |
C17 | 0.0659 (10) | 0.0439 (8) | 0.0553 (9) | 0.0126 (7) | −0.0089 (8) | 0.0021 (7) |
C18 | 0.0383 (7) | 0.0537 (8) | 0.0397 (6) | 0.0043 (6) | 0.0039 (5) | 0.0015 (6) |
C19 | 0.0502 (8) | 0.0452 (8) | 0.0521 (8) | 0.0014 (6) | −0.0001 (7) | −0.0062 (6) |
C20 | 0.0476 (8) | 0.0415 (8) | 0.0558 (8) | 0.0054 (6) | −0.0015 (7) | 0.0037 (6) |
C21 | 0.0509 (9) | 0.0859 (13) | 0.0483 (8) | 0.0029 (9) | −0.0013 (7) | −0.0147 (8) |
N1 | 0.0325 (6) | 0.0506 (7) | 0.0432 (6) | −0.0013 (5) | 0.0028 (4) | 0.0065 (5) |
O1 | 0.0384 (5) | 0.0636 (7) | 0.0520 (6) | −0.0094 (5) | 0.0083 (4) | −0.0003 (5) |
O2 | 0.0631 (7) | 0.0654 (7) | 0.0461 (6) | 0.0108 (6) | −0.0111 (5) | −0.0018 (5) |
S1 | 0.0508 (2) | 0.0384 (2) | 0.0756 (3) | −0.00997 (16) | 0.00913 (19) | −0.00040 (17) |
C1—N1 | 1.4622 (17) | C11—H11 | 0.9300 |
C1—C9 | 1.522 (2) | C12—C13 | 1.374 (2) |
C1—S1 | 1.8192 (15) | C12—H12 | 0.9300 |
C1—H1 | 0.9800 | C13—C14 | 1.376 (2) |
C2—O1 | 1.2240 (16) | C13—H13 | 0.9300 |
C2—N1 | 1.3591 (18) | C14—H14 | 0.9300 |
C2—C3 | 1.4929 (18) | C15—C20 | 1.369 (2) |
C3—C8 | 1.389 (2) | C15—C16 | 1.380 (2) |
C3—C4 | 1.398 (2) | C15—N1 | 1.4432 (17) |
C4—C5 | 1.398 (2) | C16—C17 | 1.380 (2) |
C4—S1 | 1.7533 (16) | C16—H16 | 0.9300 |
C5—C6 | 1.367 (3) | C17—C18 | 1.384 (2) |
C5—H5 | 0.9300 | C17—H17 | 0.9300 |
C6—C7 | 1.385 (3) | C18—O2 | 1.3661 (17) |
C6—H6 | 0.9300 | C18—C19 | 1.374 (2) |
C7—C8 | 1.378 (2) | C19—C20 | 1.390 (2) |
C7—H7 | 0.9300 | C19—H19 | 0.9300 |
C8—H8 | 0.9300 | C20—H20 | 0.9300 |
C9—C10 | 1.383 (2) | C21—O2 | 1.427 (2) |
C9—C14 | 1.3935 (19) | C21—H21A | 0.9600 |
C10—C11 | 1.386 (2) | C21—H21B | 0.9600 |
C10—H10 | 0.9300 | C21—H21C | 0.9600 |
C11—C12 | 1.376 (2) | ||
N1—C1—C9 | 114.51 (11) | C13—C12—H12 | 120.2 |
N1—C1—S1 | 110.61 (10) | C11—C12—H12 | 120.2 |
C9—C1—S1 | 113.29 (9) | C12—C13—C14 | 120.51 (15) |
N1—C1—H1 | 105.9 | C12—C13—H13 | 119.7 |
C9—C1—H1 | 105.9 | C14—C13—H13 | 119.7 |
S1—C1—H1 | 105.9 | C13—C14—C9 | 120.56 (15) |
O1—C2—N1 | 121.40 (12) | C13—C14—H14 | 119.7 |
O1—C2—C3 | 121.02 (12) | C9—C14—H14 | 119.7 |
N1—C2—C3 | 117.56 (12) | C20—C15—C16 | 119.35 (13) |
C8—C3—C4 | 118.99 (13) | C20—C15—N1 | 121.54 (12) |
C8—C3—C2 | 117.78 (13) | C16—C15—N1 | 119.10 (12) |
C4—C3—C2 | 122.92 (13) | C15—C16—C17 | 120.20 (14) |
C5—C4—C3 | 119.71 (15) | C15—C16—H16 | 119.9 |
C5—C4—S1 | 119.37 (13) | C17—C16—H16 | 119.9 |
C3—C4—S1 | 120.89 (11) | C16—C17—C18 | 120.24 (14) |
C6—C5—C4 | 120.15 (17) | C16—C17—H17 | 119.9 |
C6—C5—H5 | 119.9 | C18—C17—H17 | 119.9 |
C4—C5—H5 | 119.9 | O2—C18—C19 | 124.93 (14) |
C5—C6—C7 | 120.48 (16) | O2—C18—C17 | 115.38 (13) |
C5—C6—H6 | 119.8 | C19—C18—C17 | 119.68 (13) |
C7—C6—H6 | 119.8 | C18—C19—C20 | 119.59 (14) |
C8—C7—C6 | 119.88 (17) | C18—C19—H19 | 120.2 |
C8—C7—H7 | 120.1 | C20—C19—H19 | 120.2 |
C6—C7—H7 | 120.1 | C15—C20—C19 | 120.91 (14) |
C7—C8—C3 | 120.71 (16) | C15—C20—H20 | 119.5 |
C7—C8—H8 | 119.6 | C19—C20—H20 | 119.5 |
C3—C8—H8 | 119.6 | O2—C21—H21A | 109.5 |
C10—C9—C14 | 118.62 (14) | O2—C21—H21B | 109.5 |
C10—C9—C1 | 123.11 (12) | H21A—C21—H21B | 109.5 |
C14—C9—C1 | 118.24 (13) | O2—C21—H21C | 109.5 |
C9—C10—C11 | 120.31 (14) | H21A—C21—H21C | 109.5 |
C9—C10—H10 | 119.8 | H21B—C21—H21C | 109.5 |
C11—C10—H10 | 119.8 | C2—N1—C15 | 119.41 (11) |
C12—C11—C10 | 120.50 (15) | C2—N1—C1 | 123.07 (11) |
C12—C11—H11 | 119.8 | C15—N1—C1 | 117.51 (10) |
C10—C11—H11 | 119.8 | C18—O2—C21 | 118.24 (13) |
C13—C12—C11 | 119.50 (16) | C4—S1—C1 | 96.84 (7) |
O1—C2—C3—C8 | −20.9 (2) | N1—C15—C16—C17 | −177.27 (15) |
N1—C2—C3—C8 | 161.10 (13) | C15—C16—C17—C18 | −0.1 (3) |
O1—C2—C3—C4 | 152.55 (14) | C16—C17—C18—O2 | 178.86 (16) |
N1—C2—C3—C4 | −25.42 (19) | C16—C17—C18—C19 | −1.3 (3) |
C8—C3—C4—C5 | 2.6 (2) | O2—C18—C19—C20 | −178.67 (14) |
C2—C3—C4—C5 | −170.80 (13) | C17—C18—C19—C20 | 1.5 (2) |
C8—C3—C4—S1 | −179.16 (11) | C16—C15—C20—C19 | −1.2 (2) |
C2—C3—C4—S1 | 7.43 (18) | N1—C15—C20—C19 | 177.45 (13) |
C3—C4—C5—C6 | −1.7 (2) | C18—C19—C20—C15 | −0.3 (2) |
S1—C4—C5—C6 | −179.94 (13) | O1—C2—N1—C15 | −6.1 (2) |
C4—C5—C6—C7 | −0.8 (3) | C3—C2—N1—C15 | 171.89 (12) |
C5—C6—C7—C8 | 2.4 (3) | O1—C2—N1—C1 | 175.13 (13) |
C6—C7—C8—C3 | −1.5 (3) | C3—C2—N1—C1 | −6.91 (19) |
C4—C3—C8—C7 | −1.0 (2) | C20—C15—N1—C2 | 86.36 (17) |
C2—C3—C8—C7 | 172.71 (14) | C16—C15—N1—C2 | −95.04 (17) |
N1—C1—C9—C10 | 3.89 (19) | C20—C15—N1—C1 | −94.78 (16) |
S1—C1—C9—C10 | −124.24 (13) | C16—C15—N1—C1 | 83.83 (17) |
N1—C1—C9—C14 | −173.97 (12) | C9—C1—N1—C2 | −80.00 (16) |
S1—C1—C9—C14 | 57.90 (15) | S1—C1—N1—C2 | 49.48 (16) |
C14—C9—C10—C11 | 0.1 (2) | C9—C1—N1—C15 | 101.18 (14) |
C1—C9—C10—C11 | −177.71 (14) | S1—C1—N1—C15 | −129.34 (11) |
C9—C10—C11—C12 | 0.1 (3) | C19—C18—O2—C21 | 0.1 (2) |
C10—C11—C12—C13 | −0.2 (3) | C17—C18—O2—C21 | 179.91 (15) |
C11—C12—C13—C14 | 0.0 (3) | C5—C4—S1—C1 | −152.63 (12) |
C12—C13—C14—C9 | 0.3 (2) | C3—C4—S1—C1 | 29.14 (12) |
C10—C9—C14—C13 | −0.3 (2) | N1—C1—S1—C4 | −54.14 (10) |
C1—C9—C14—C13 | 177.63 (13) | C9—C1—S1—C4 | 75.99 (10) |
C20—C15—C16—C17 | 1.4 (2) |
Cg(X) = center of gravity of ring (X); D—H···CgX = angle of the D—H bond with the π plane |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.59 | 3.447 (2) | 154 |
C21—H21B···O1ii | 0.96 | 2.63 | 3.352 (2) | 132 |
C5—H5···O2iii | 0.93 | 2.46 | 3.387 (2) | 173 |
C21—H21A···Cg4iv | 0.96 | 2.96 | 3.8068 (10) | 148 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+3/2, y+3/2, z+1. |
2C21H14F3NOS·C7H8 | Dx = 1.371 Mg m−3 |
Mr = 862.92 | Melting point = 404–406 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.953 (2) Å | Cell parameters from 6665 reflections |
b = 14.516 (3) Å | θ = 2.2–28.2° |
c = 24.546 (5) Å | µ = 0.20 mm−1 |
β = 101.024 (4)° | T = 298 K |
V = 4180.5 (14) Å3 | Needle, colourless |
Z = 4 | 0.29 × 0.09 × 0.07 mm |
F(000) = 1784 |
Bruker CCD area-detector diffractometer | 10359 independent reflections |
Radiation source: fine-focus sealed tube | 8329 reflections with I > 2˘I) |
Graphite monochromator | Rint = 0.052 |
phi and ω scans | θmax = 28.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→15 |
Tmin = 0.592, Tmax = 0.920 | k = −19→19 |
39335 measured reflections | l = −32→32 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.133 | H-atom parameters constrained |
wR(F2) = 0.240 | w = 1/[σ2(Fo2) + (0.0482P)2 + 8.2026P] where P = (Fo2 + 2Fc2)/3 |
S = 1.31 | (Δ/σ)max = 0.001 |
10359 reflections | Δρmax = 0.48 e Å−3 |
580 parameters | Δρmin = −0.34 e Å−3 |
74 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0015 (2) |
Experimental. Absorption correction: SADABS (Bruker, 2001) was used for absorption correction. R(int) was 0.0709 before and 0.0303 after correction. The Ratio of minimum to maximum transmission is 0.5920. The λ/2 correction factor is 0.0015. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm. |
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. |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.7415 (3) | 1.0190 (3) | 0.11278 (17) | 0.0326 (9) | |
H1 | 0.6834 | 0.9719 | 0.1005 | 0.039* | |
C2 | 0.9318 (3) | 1.0494 (3) | 0.09051 (15) | 0.0292 (8) | |
C3 | 0.9144 (3) | 1.1495 (3) | 0.10152 (15) | 0.0296 (9) | |
C4 | 0.8087 (4) | 1.1904 (3) | 0.09618 (16) | 0.0347 (9) | |
C5 | 0.8013 (5) | 1.2859 (3) | 0.10036 (19) | 0.0498 (12) | |
H5 | 0.7301 | 1.3140 | 0.0959 | 0.060* | |
C6 | 0.8979 (5) | 1.3387 (3) | 0.1109 (2) | 0.0597 (15) | |
H6 | 0.8919 | 1.4024 | 0.1134 | 0.072* | |
C7 | 1.0031 (5) | 1.2988 (3) | 0.1178 (2) | 0.0549 (14) | |
H7 | 1.0684 | 1.3350 | 0.1257 | 0.066* | |
C8 | 1.0120 (4) | 1.2042 (3) | 0.11295 (18) | 0.0417 (11) | |
H8 | 1.0836 | 1.1770 | 0.1173 | 0.050* | |
C9 | 0.7581 (4) | 1.0210 (3) | 0.17549 (17) | 0.0374 (10) | |
C10 | 0.6620 (5) | 1.0249 (4) | 0.1991 (2) | 0.0641 (16) | |
H10 | 0.5901 | 1.0276 | 0.1765 | 0.077* | |
C11 | 0.6725 (8) | 1.0247 (5) | 0.2565 (3) | 0.094 (3) | |
H11 | 0.6076 | 1.0267 | 0.2721 | 0.113* | |
C12 | 0.7777 (8) | 1.0216 (5) | 0.2900 (3) | 0.095 (3) | |
H12 | 0.7841 | 1.0226 | 0.3284 | 0.114* | |
C13 | 0.8724 (6) | 1.0169 (4) | 0.2676 (2) | 0.0735 (18) | |
H13 | 0.9440 | 1.0139 | 0.2904 | 0.088* | |
C14 | 0.8622 (5) | 1.0166 (4) | 0.21027 (19) | 0.0520 (13) | |
H14 | 0.9277 | 1.0134 | 0.1951 | 0.062* | |
C15 | 0.8522 (3) | 0.8954 (3) | 0.07876 (15) | 0.0287 (8) | |
C16 | 0.8250 (4) | 0.8292 (3) | 0.11498 (18) | 0.0410 (11) | |
H16 | 0.7999 | 0.8472 | 0.1470 | 0.049* | |
C17 | 0.8350 (4) | 0.7373 (3) | 0.10367 (19) | 0.0449 (11) | |
H17 | 0.8168 | 0.6931 | 0.1280 | 0.054* | |
C18 | 0.8718 (4) | 0.7104 (3) | 0.05646 (18) | 0.0368 (10) | |
C19 | 0.8959 (3) | 0.7756 (3) | 0.01947 (17) | 0.0325 (9) | |
H19 | 0.9187 | 0.7571 | −0.0130 | 0.039* | |
C20 | 0.8862 (3) | 0.8678 (3) | 0.03046 (15) | 0.0307 (9) | |
H20 | 0.9024 | 0.9117 | 0.0054 | 0.037* | |
C21 | 0.8898 (5) | 0.6098 (3) | 0.0469 (2) | 0.0543 (13) | |
F1 | 0.8004 (3) | 0.5593 (2) | 0.05201 (19) | 0.0934 (13) | |
F2 | 0.9121 (5) | 0.5909 (2) | −0.00173 (17) | 0.1125 (17) | |
F3 | 0.9745 (3) | 0.5749 (2) | 0.08345 (19) | 0.1020 (15) | |
N1 | 0.8416 (3) | 0.9909 (2) | 0.09121 (13) | 0.0287 (7) | |
O1 | 1.0226 (2) | 1.0219 (2) | 0.08167 (14) | 0.0426 (8) | |
S1 | 0.68361 (9) | 1.12577 (9) | 0.08114 (5) | 0.0443 (3) | |
C22 | 0.2359 (3) | 0.8724 (3) | 0.09757 (16) | 0.0312 (9) | |
H22 | 0.1793 | 0.9219 | 0.0944 | 0.037* | |
C23 | 0.4274 (3) | 0.8614 (3) | 0.07246 (14) | 0.0259 (8) | |
C24 | 0.4087 (3) | 0.7606 (3) | 0.06289 (15) | 0.0288 (8) | |
C25 | 0.3015 (4) | 0.7208 (3) | 0.05029 (16) | 0.0361 (10) | |
C26 | 0.2912 (5) | 0.6259 (3) | 0.0385 (2) | 0.0514 (13) | |
H26 | 0.2197 | 0.5985 | 0.0300 | 0.062* | |
C27 | 0.3874 (5) | 0.5744 (3) | 0.0397 (2) | 0.0595 (15) | |
H27 | 0.3805 | 0.5118 | 0.0317 | 0.071* | |
C28 | 0.4935 (5) | 0.6129 (3) | 0.0526 (2) | 0.0548 (13) | |
H28 | 0.5580 | 0.5766 | 0.0534 | 0.066* | |
C29 | 0.5046 (4) | 0.7060 (3) | 0.06431 (18) | 0.0397 (10) | |
H29 | 0.5767 | 0.7323 | 0.0732 | 0.048* | |
C30 | 0.2498 (4) | 0.8357 (3) | 0.15572 (18) | 0.0370 (10) | |
C35 | 0.1522 (5) | 0.8182 (5) | 0.1762 (3) | 0.0771 (19) | |
H35 | 0.0811 | 0.8304 | 0.1544 | 0.093* | |
C34 | 0.1596 (8) | 0.7825 (6) | 0.2291 (4) | 0.110 (3) | |
H34 | 0.0937 | 0.7719 | 0.2431 | 0.132* | |
C33 | 0.2635 (9) | 0.7628 (5) | 0.2606 (3) | 0.102 (3) | |
H33 | 0.2683 | 0.7372 | 0.2957 | 0.123* | |
C32 | 0.3592 (7) | 0.7803 (5) | 0.2412 (2) | 0.084 (2) | |
H32 | 0.4299 | 0.7672 | 0.2631 | 0.101* | |
C31 | 0.3528 (5) | 0.8178 (4) | 0.18866 (19) | 0.0548 (14) | |
H31 | 0.4194 | 0.8308 | 0.1758 | 0.066* | |
C36 | 0.3509 (3) | 1.0108 (3) | 0.08862 (15) | 0.0273 (8) | |
C37 | 0.3283 (4) | 1.0558 (3) | 0.13476 (17) | 0.0393 (10) | |
H37 | 0.3061 | 1.0225 | 0.1633 | 0.047* | |
C38 | 0.3386 (4) | 1.1501 (3) | 0.13847 (19) | 0.0435 (11) | |
H38 | 0.3236 | 1.1804 | 0.1697 | 0.052* | |
C39 | 0.3709 (3) | 1.1997 (3) | 0.09650 (17) | 0.0341 (9) | |
C40 | 0.3922 (3) | 1.1551 (3) | 0.04987 (16) | 0.0328 (9) | |
H40 | 0.4134 | 1.1888 | 0.0213 | 0.039* | |
C41 | 0.3820 (3) | 1.0614 (3) | 0.04573 (16) | 0.0305 (9) | |
H41 | 0.3959 | 1.0315 | 0.0142 | 0.037* | |
C42 | 0.3831 (5) | 1.3022 (3) | 0.1012 (2) | 0.0516 (13) | |
F6A | 0.308 (2) | 1.3467 (7) | 0.0659 (11) | 0.155 (13) | 0.57 (3) |
F5A | 0.378 (3) | 1.3360 (6) | 0.1506 (5) | 0.104 (7) | 0.57 (3) |
F4A | 0.4828 (13) | 1.3323 (8) | 0.0936 (12) | 0.112 (9) | 0.57 (3) |
N2 | 0.3391 (3) | 0.9132 (2) | 0.08403 (13) | 0.0271 (7) | |
O2 | 0.5195 (2) | 0.89607 (19) | 0.06948 (12) | 0.0364 (7) | |
S2 | 0.17800 (9) | 0.78640 (9) | 0.04611 (5) | 0.0457 (3) | |
F4B | 0.474 (2) | 1.3253 (11) | 0.1315 (15) | 0.138 (16) | 0.43 (3) |
F5B | 0.383 (3) | 1.3413 (10) | 0.0544 (8) | 0.109 (12) | 0.43 (3) |
F6B | 0.301 (2) | 1.3415 (7) | 0.1170 (15) | 0.106 (10) | 0.43 (3) |
C43 | 0.6833 (6) | 0.7489 (4) | 0.2230 (2) | 0.0640 (16) | |
H43 | 0.6441 | 0.8046 | 0.2200 | 0.077* | |
C44 | 0.7974 (6) | 0.7450 (5) | 0.2477 (2) | 0.0703 (18) | |
H44 | 0.8358 | 0.7984 | 0.2613 | 0.084* | |
C45 | 0.8531 (6) | 0.6628 (5) | 0.2521 (2) | 0.0708 (17) | |
H45 | 0.9297 | 0.6606 | 0.2689 | 0.085* | |
C46 | 0.7985 (5) | 0.5832 (5) | 0.2322 (2) | 0.0657 (16) | |
H46 | 0.8378 | 0.5276 | 0.2355 | 0.079* | |
C47 | 0.6844 (5) | 0.5861 (4) | 0.2072 (2) | 0.0599 (15) | |
C48 | 0.6283 (5) | 0.6680 (4) | 0.2028 (2) | 0.0582 (14) | |
H48 | 0.5517 | 0.6699 | 0.1860 | 0.070* | |
C49 | 0.6264 (8) | 0.4992 (5) | 0.1851 (4) | 0.112 (3) | |
H49A | 0.6040 | 0.4655 | 0.2149 | 0.168* | |
H49B | 0.6778 | 0.4625 | 0.1686 | 0.168* | |
H49C | 0.5602 | 0.5137 | 0.1577 | 0.168* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.026 (2) | 0.030 (2) | 0.044 (2) | −0.0063 (17) | 0.0144 (17) | −0.0091 (18) |
C2 | 0.031 (2) | 0.031 (2) | 0.0272 (19) | 0.0012 (17) | 0.0082 (16) | 0.0014 (16) |
C3 | 0.036 (2) | 0.027 (2) | 0.0263 (19) | −0.0033 (17) | 0.0092 (16) | 0.0029 (16) |
C4 | 0.044 (2) | 0.031 (2) | 0.027 (2) | 0.0055 (19) | 0.0029 (18) | −0.0022 (17) |
C5 | 0.070 (3) | 0.036 (3) | 0.045 (3) | 0.015 (3) | 0.013 (2) | 0.003 (2) |
C6 | 0.098 (5) | 0.030 (3) | 0.055 (3) | −0.008 (3) | 0.025 (3) | 0.001 (2) |
C7 | 0.068 (4) | 0.038 (3) | 0.059 (3) | −0.021 (3) | 0.014 (3) | −0.002 (2) |
C8 | 0.048 (3) | 0.040 (3) | 0.037 (2) | −0.012 (2) | 0.008 (2) | 0.006 (2) |
C9 | 0.046 (3) | 0.029 (2) | 0.044 (2) | −0.0076 (19) | 0.024 (2) | −0.0083 (19) |
C10 | 0.067 (4) | 0.060 (4) | 0.079 (4) | −0.008 (3) | 0.048 (3) | −0.013 (3) |
C11 | 0.129 (7) | 0.082 (5) | 0.097 (6) | −0.012 (5) | 0.088 (5) | −0.012 (4) |
C12 | 0.163 (8) | 0.078 (5) | 0.060 (4) | −0.021 (6) | 0.060 (5) | −0.006 (4) |
C13 | 0.105 (5) | 0.072 (4) | 0.042 (3) | −0.015 (4) | 0.011 (3) | 0.005 (3) |
C14 | 0.063 (3) | 0.056 (3) | 0.039 (3) | −0.011 (3) | 0.014 (2) | 0.004 (2) |
C15 | 0.0273 (19) | 0.028 (2) | 0.032 (2) | −0.0021 (16) | 0.0086 (16) | −0.0029 (16) |
C16 | 0.055 (3) | 0.034 (2) | 0.040 (2) | −0.005 (2) | 0.025 (2) | −0.0040 (19) |
C17 | 0.057 (3) | 0.032 (2) | 0.049 (3) | −0.006 (2) | 0.019 (2) | 0.003 (2) |
C18 | 0.033 (2) | 0.029 (2) | 0.048 (3) | −0.0012 (18) | 0.0060 (19) | −0.0052 (19) |
C19 | 0.029 (2) | 0.035 (2) | 0.035 (2) | −0.0013 (18) | 0.0089 (17) | −0.0079 (18) |
C20 | 0.030 (2) | 0.034 (2) | 0.0288 (19) | −0.0029 (18) | 0.0076 (16) | 0.0001 (17) |
C21 | 0.061 (3) | 0.031 (3) | 0.069 (4) | 0.000 (2) | 0.011 (3) | −0.005 (2) |
F1 | 0.080 (3) | 0.0350 (17) | 0.166 (4) | −0.0179 (17) | 0.025 (3) | −0.019 (2) |
F2 | 0.206 (5) | 0.047 (2) | 0.101 (3) | 0.028 (3) | 0.071 (3) | −0.014 (2) |
F3 | 0.095 (3) | 0.0451 (19) | 0.144 (4) | 0.0244 (19) | −0.032 (3) | −0.003 (2) |
N1 | 0.0263 (17) | 0.0288 (17) | 0.0338 (17) | −0.0029 (14) | 0.0126 (14) | −0.0020 (14) |
O1 | 0.0307 (16) | 0.0365 (17) | 0.065 (2) | −0.0004 (13) | 0.0208 (15) | 0.0002 (15) |
S1 | 0.0308 (6) | 0.0465 (7) | 0.0526 (7) | 0.0113 (5) | 0.0007 (5) | −0.0057 (6) |
C22 | 0.026 (2) | 0.028 (2) | 0.043 (2) | 0.0014 (17) | 0.0153 (17) | −0.0001 (18) |
C23 | 0.0272 (19) | 0.030 (2) | 0.0219 (17) | −0.0002 (16) | 0.0078 (15) | −0.0006 (15) |
C24 | 0.037 (2) | 0.0222 (19) | 0.0273 (19) | 0.0016 (17) | 0.0065 (16) | −0.0013 (15) |
C25 | 0.044 (2) | 0.034 (2) | 0.029 (2) | −0.009 (2) | 0.0050 (18) | −0.0046 (18) |
C26 | 0.065 (3) | 0.041 (3) | 0.047 (3) | −0.022 (3) | 0.007 (2) | −0.009 (2) |
C27 | 0.092 (5) | 0.030 (3) | 0.058 (3) | −0.003 (3) | 0.019 (3) | −0.009 (2) |
C28 | 0.076 (4) | 0.031 (3) | 0.061 (3) | 0.015 (3) | 0.021 (3) | 0.000 (2) |
C29 | 0.046 (3) | 0.036 (2) | 0.039 (2) | 0.006 (2) | 0.014 (2) | −0.0002 (19) |
C30 | 0.047 (3) | 0.026 (2) | 0.046 (2) | −0.0053 (19) | 0.028 (2) | 0.0014 (18) |
C35 | 0.074 (4) | 0.089 (5) | 0.082 (4) | −0.026 (4) | 0.049 (4) | −0.003 (4) |
C34 | 0.146 (8) | 0.101 (6) | 0.113 (7) | −0.037 (6) | 0.101 (6) | 0.005 (5) |
C33 | 0.215 (11) | 0.047 (4) | 0.067 (5) | −0.005 (5) | 0.083 (6) | 0.009 (3) |
C32 | 0.133 (6) | 0.077 (4) | 0.047 (3) | 0.038 (4) | 0.028 (4) | 0.017 (3) |
C31 | 0.071 (4) | 0.060 (3) | 0.037 (3) | 0.016 (3) | 0.021 (2) | 0.013 (2) |
C36 | 0.0263 (19) | 0.027 (2) | 0.0291 (19) | 0.0026 (16) | 0.0066 (15) | 0.0038 (16) |
C37 | 0.054 (3) | 0.034 (2) | 0.036 (2) | 0.003 (2) | 0.023 (2) | 0.0026 (18) |
C38 | 0.060 (3) | 0.033 (2) | 0.043 (2) | 0.004 (2) | 0.022 (2) | −0.010 (2) |
C39 | 0.035 (2) | 0.026 (2) | 0.042 (2) | 0.0013 (18) | 0.0074 (18) | −0.0025 (18) |
C40 | 0.034 (2) | 0.032 (2) | 0.034 (2) | 0.0029 (18) | 0.0098 (17) | 0.0094 (17) |
C41 | 0.034 (2) | 0.031 (2) | 0.0288 (19) | 0.0031 (17) | 0.0105 (17) | −0.0001 (16) |
C42 | 0.063 (4) | 0.035 (3) | 0.057 (3) | −0.005 (3) | 0.010 (3) | −0.003 (2) |
F6A | 0.166 (17) | 0.036 (4) | 0.20 (2) | 0.001 (9) | −0.125 (16) | 0.018 (11) |
F5A | 0.20 (2) | 0.038 (4) | 0.084 (7) | −0.002 (8) | 0.062 (10) | −0.020 (4) |
F4A | 0.096 (12) | 0.053 (6) | 0.21 (2) | −0.034 (7) | 0.078 (15) | −0.037 (11) |
N2 | 0.0268 (16) | 0.0257 (16) | 0.0306 (17) | 0.0005 (14) | 0.0098 (13) | 0.0017 (13) |
O2 | 0.0318 (15) | 0.0311 (15) | 0.0500 (18) | −0.0044 (13) | 0.0170 (13) | −0.0068 (13) |
S2 | 0.0273 (5) | 0.0535 (7) | 0.0526 (7) | −0.0094 (5) | −0.0015 (5) | −0.0055 (6) |
F4B | 0.14 (2) | 0.048 (6) | 0.18 (3) | −0.020 (11) | −0.085 (19) | −0.028 (14) |
F5B | 0.22 (3) | 0.029 (5) | 0.086 (12) | −0.007 (13) | 0.060 (17) | 0.007 (6) |
F6B | 0.117 (15) | 0.037 (5) | 0.18 (3) | 0.028 (7) | 0.081 (16) | −0.016 (11) |
C43 | 0.087 (4) | 0.069 (4) | 0.040 (3) | 0.004 (3) | 0.021 (3) | 0.016 (3) |
C44 | 0.090 (5) | 0.080 (5) | 0.041 (3) | −0.032 (4) | 0.015 (3) | 0.002 (3) |
C45 | 0.066 (4) | 0.098 (5) | 0.048 (3) | −0.010 (4) | 0.008 (3) | 0.008 (3) |
C46 | 0.072 (4) | 0.079 (4) | 0.048 (3) | 0.019 (3) | 0.016 (3) | 0.017 (3) |
C47 | 0.072 (4) | 0.061 (4) | 0.048 (3) | −0.008 (3) | 0.013 (3) | 0.014 (3) |
C48 | 0.056 (3) | 0.072 (4) | 0.046 (3) | 0.004 (3) | 0.007 (2) | 0.018 (3) |
C49 | 0.131 (7) | 0.080 (5) | 0.124 (7) | −0.012 (5) | 0.026 (6) | 0.010 (5) |
C1—H1 | 0.9800 | C25—C26 | 1.407 (6) |
C1—C9 | 1.514 (6) | C25—S2 | 1.743 (5) |
C1—N1 | 1.456 (5) | C26—H26 | 0.9300 |
C1—S1 | 1.811 (4) | C26—C27 | 1.367 (7) |
C2—C3 | 1.501 (5) | C27—H27 | 0.9300 |
C2—N1 | 1.375 (5) | C27—C28 | 1.367 (7) |
C2—O1 | 1.215 (4) | C28—H28 | 0.9300 |
C3—C4 | 1.379 (5) | C28—C29 | 1.384 (6) |
C3—C8 | 1.395 (6) | C29—H29 | 0.9300 |
C4—C5 | 1.394 (6) | C30—C35 | 1.379 (6) |
C4—S1 | 1.744 (4) | C30—C31 | 1.362 (6) |
C5—H5 | 0.9300 | C35—H35 | 0.9300 |
C5—C6 | 1.369 (7) | C35—C34 | 1.386 (9) |
C6—H6 | 0.9300 | C34—H34 | 0.9300 |
C6—C7 | 1.365 (7) | C34—C33 | 1.362 (10) |
C7—H7 | 0.9300 | C33—H33 | 0.9300 |
C7—C8 | 1.384 (6) | C33—C32 | 1.344 (10) |
C8—H8 | 0.9300 | C32—H32 | 0.9300 |
C9—C10 | 1.383 (6) | C32—C31 | 1.389 (7) |
C9—C14 | 1.369 (6) | C31—H31 | 0.9300 |
C10—H10 | 0.9300 | C36—C37 | 1.378 (5) |
C10—C11 | 1.390 (8) | C36—C41 | 1.391 (5) |
C11—H11 | 0.9300 | C36—N2 | 1.425 (5) |
C11—C12 | 1.365 (10) | C37—H37 | 0.9300 |
C12—H12 | 0.9300 | C37—C38 | 1.376 (6) |
C12—C13 | 1.353 (9) | C38—H38 | 0.9300 |
C13—H13 | 0.9300 | C38—C39 | 1.371 (6) |
C13—C14 | 1.388 (7) | C39—C40 | 1.380 (5) |
C14—H14 | 0.9300 | C39—C42 | 1.497 (6) |
C15—C16 | 1.390 (5) | C40—H40 | 0.9300 |
C15—C20 | 1.383 (5) | C40—C41 | 1.368 (5) |
C15—N1 | 1.430 (5) | C41—H41 | 0.9300 |
C16—H16 | 0.9300 | C42—F6A | 1.292 (9) |
C16—C17 | 1.373 (6) | C42—F5A | 1.321 (9) |
C17—H17 | 0.9300 | C42—F4A | 1.316 (10) |
C17—C18 | 1.372 (6) | C42—F4B | 1.239 (15) |
C18—C19 | 1.379 (6) | C42—F5B | 1.283 (15) |
C18—C21 | 1.501 (6) | C42—F6B | 1.262 (12) |
C19—H19 | 0.9300 | C43—H43 | 0.9300 |
C19—C20 | 1.375 (5) | C43—C44 | 1.383 (9) |
C20—H20 | 0.9300 | C43—C48 | 1.390 (8) |
C21—F1 | 1.321 (6) | C44—H44 | 0.9300 |
C21—F2 | 1.301 (6) | C44—C45 | 1.360 (9) |
C21—F3 | 1.318 (6) | C45—H45 | 0.9300 |
C22—H22 | 0.9800 | C45—C46 | 1.371 (9) |
C22—C30 | 1.503 (5) | C46—H46 | 0.9300 |
C22—N2 | 1.463 (5) | C46—C47 | 1.385 (8) |
C22—S2 | 1.816 (4) | C47—C48 | 1.358 (8) |
C23—C24 | 1.493 (5) | C47—C49 | 1.491 (9) |
C23—N2 | 1.370 (5) | C48—H48 | 0.9300 |
C23—O2 | 1.225 (4) | C49—H49A | 0.9600 |
C24—C25 | 1.386 (5) | C49—H49B | 0.9600 |
C24—C29 | 1.388 (6) | C49—H49C | 0.9600 |
C9—C1—H1 | 106.0 | C25—C26—H26 | 120.3 |
C9—C1—S1 | 112.6 (3) | C27—C26—C25 | 119.4 (5) |
N1—C1—H1 | 106.0 | C27—C26—H26 | 120.3 |
N1—C1—C9 | 114.7 (3) | C26—C27—H27 | 119.3 |
N1—C1—S1 | 110.9 (3) | C28—C27—C26 | 121.4 (5) |
S1—C1—H1 | 106.0 | C28—C27—H27 | 119.3 |
N1—C2—C3 | 117.4 (3) | C27—C28—H28 | 120.2 |
O1—C2—C3 | 120.6 (4) | C27—C28—C29 | 119.6 (5) |
O1—C2—N1 | 122.0 (4) | C29—C28—H28 | 120.2 |
C4—C3—C2 | 123.8 (4) | C24—C29—H29 | 119.8 |
C4—C3—C8 | 119.4 (4) | C28—C29—C24 | 120.5 (5) |
C8—C3—C2 | 116.6 (4) | C28—C29—H29 | 119.8 |
C3—C4—C5 | 119.4 (4) | C35—C30—C22 | 117.6 (5) |
C3—C4—S1 | 121.4 (3) | C31—C30—C22 | 123.7 (4) |
C5—C4—S1 | 119.1 (4) | C31—C30—C35 | 118.7 (5) |
C4—C5—H5 | 119.8 | C30—C35—H35 | 119.9 |
C6—C5—C4 | 120.5 (5) | C30—C35—C34 | 120.2 (7) |
C6—C5—H5 | 119.8 | C34—C35—H35 | 119.9 |
C5—C6—H6 | 119.7 | C35—C34—H34 | 120.0 |
C7—C6—C5 | 120.7 (5) | C33—C34—C35 | 119.9 (6) |
C7—C6—H6 | 119.7 | C33—C34—H34 | 120.0 |
C6—C7—H7 | 120.2 | C34—C33—H33 | 119.8 |
C6—C7—C8 | 119.7 (5) | C32—C33—C34 | 120.3 (6) |
C8—C7—H7 | 120.2 | C32—C33—H33 | 119.8 |
C3—C8—H8 | 119.8 | C33—C32—H32 | 119.9 |
C7—C8—C3 | 120.4 (5) | C33—C32—C31 | 120.2 (7) |
C7—C8—H8 | 119.8 | C31—C32—H32 | 119.9 |
C10—C9—C1 | 117.9 (4) | C30—C31—C32 | 120.6 (5) |
C14—C9—C1 | 124.1 (4) | C30—C31—H31 | 119.7 |
C14—C9—C10 | 118.0 (5) | C32—C31—H31 | 119.7 |
C9—C10—H10 | 119.9 | C37—C36—C41 | 119.6 (4) |
C9—C10—C11 | 120.1 (6) | C37—C36—N2 | 120.3 (3) |
C11—C10—H10 | 119.9 | C41—C36—N2 | 120.1 (3) |
C10—C11—H11 | 119.8 | C36—C37—H37 | 120.1 |
C12—C11—C10 | 120.4 (6) | C38—C37—C36 | 119.8 (4) |
C12—C11—H11 | 119.8 | C38—C37—H37 | 120.1 |
C11—C12—H12 | 120.0 | C37—C38—H38 | 119.8 |
C13—C12—C11 | 120.1 (6) | C39—C38—C37 | 120.5 (4) |
C13—C12—H12 | 120.0 | C39—C38—H38 | 119.8 |
C12—C13—H13 | 120.2 | C38—C39—C40 | 120.0 (4) |
C12—C13—C14 | 119.6 (6) | C38—C39—C42 | 120.1 (4) |
C14—C13—H13 | 120.2 | C40—C39—C42 | 120.0 (4) |
C9—C14—C13 | 121.7 (5) | C39—C40—H40 | 120.0 |
C9—C14—H14 | 119.2 | C41—C40—C39 | 120.0 (4) |
C13—C14—H14 | 119.2 | C41—C40—H40 | 120.0 |
C16—C15—N1 | 119.5 (3) | C36—C41—H41 | 119.9 |
C20—C15—C16 | 119.4 (4) | C40—C41—C36 | 120.1 (4) |
C20—C15—N1 | 121.1 (3) | C40—C41—H41 | 119.9 |
C15—C16—H16 | 119.9 | F6A—C42—C39 | 113.6 (6) |
C17—C16—C15 | 120.2 (4) | F6A—C42—F5A | 106.2 (10) |
C17—C16—H16 | 119.9 | F6A—C42—F4A | 105.4 (10) |
C16—C17—H17 | 120.0 | F5A—C42—C39 | 114.8 (6) |
C18—C17—C16 | 120.1 (4) | F4A—C42—C39 | 113.4 (7) |
C18—C17—H17 | 120.0 | F4A—C42—F5A | 102.3 (8) |
C17—C18—C19 | 120.1 (4) | F4B—C42—C39 | 112.2 (9) |
C17—C18—C21 | 119.1 (4) | F4B—C42—F5B | 105.4 (14) |
C19—C18—C21 | 120.7 (4) | F4B—C42—F6B | 109.8 (13) |
C18—C19—H19 | 119.9 | F5B—C42—C39 | 112.8 (8) |
C20—C19—C18 | 120.2 (4) | F6B—C42—C39 | 113.8 (7) |
C20—C19—H19 | 119.9 | F6B—C42—F5B | 102.2 (11) |
C15—C20—H20 | 120.0 | C23—N2—C22 | 122.8 (3) |
C19—C20—C15 | 120.0 (4) | C23—N2—C36 | 119.6 (3) |
C19—C20—H20 | 120.0 | C36—N2—C22 | 117.3 (3) |
F1—C21—C18 | 112.5 (4) | C25—S2—C22 | 97.41 (18) |
F2—C21—C18 | 114.1 (4) | C44—C43—H43 | 120.6 |
F2—C21—F1 | 106.3 (5) | C44—C43—C48 | 118.7 (6) |
F2—C21—F3 | 106.2 (5) | C48—C43—H43 | 120.6 |
F3—C21—C18 | 112.5 (4) | C43—C44—H44 | 120.1 |
F3—C21—F1 | 104.6 (5) | C45—C44—C43 | 119.9 (6) |
C2—N1—C1 | 122.2 (3) | C45—C44—H44 | 120.1 |
C2—N1—C15 | 119.6 (3) | C44—C45—H45 | 119.4 |
C15—N1—C1 | 117.5 (3) | C44—C45—C46 | 121.2 (6) |
C4—S1—C1 | 97.37 (19) | C46—C45—H45 | 119.4 |
C30—C22—H22 | 106.5 | C45—C46—H46 | 120.2 |
C30—C22—S2 | 112.0 (3) | C45—C46—C47 | 119.6 (6) |
N2—C22—H22 | 106.5 | C47—C46—H46 | 120.2 |
N2—C22—C30 | 114.5 (3) | C46—C47—C49 | 119.0 (6) |
N2—C22—S2 | 110.3 (3) | C48—C47—C46 | 119.4 (6) |
S2—C22—H22 | 106.5 | C48—C47—C49 | 121.6 (6) |
N2—C23—C24 | 118.2 (3) | C43—C48—H48 | 119.4 |
O2—C23—C24 | 120.2 (3) | C47—C48—C43 | 121.2 (6) |
O2—C23—N2 | 121.6 (3) | C47—C48—H48 | 119.4 |
C25—C24—C23 | 123.3 (4) | C47—C49—H49A | 109.5 |
C25—C24—C29 | 119.4 (4) | C47—C49—H49B | 109.5 |
C29—C24—C23 | 117.2 (4) | C47—C49—H49C | 109.5 |
C24—C25—C26 | 119.6 (4) | H49A—C49—H49B | 109.5 |
C24—C25—S2 | 121.4 (3) | H49A—C49—H49C | 109.5 |
C26—C25—S2 | 118.9 (4) | H49B—C49—H49C | 109.5 |
C1—C9—C10—C11 | 178.5 (5) | C24—C25—C26—C27 | 0.1 (7) |
C1—C9—C14—C13 | −178.7 (5) | C24—C25—S2—C22 | −31.4 (4) |
C2—C3—C4—C5 | −171.8 (4) | C25—C24—C29—C28 | 0.8 (6) |
C2—C3—C4—S1 | 5.2 (5) | C25—C26—C27—C28 | 0.5 (8) |
C2—C3—C8—C7 | 173.2 (4) | C26—C25—S2—C22 | 151.0 (4) |
C3—C2—N1—C1 | −12.6 (5) | C26—C27—C28—C29 | −0.4 (8) |
C3—C2—N1—C15 | 177.5 (3) | C27—C28—C29—C24 | −0.3 (7) |
C3—C4—C5—C6 | −1.5 (7) | C29—C24—C25—C26 | −0.7 (6) |
C3—C4—S1—C1 | 28.5 (4) | C29—C24—C25—S2 | −178.3 (3) |
C4—C3—C8—C7 | −1.3 (6) | C30—C22—N2—C23 | 77.0 (4) |
C4—C5—C6—C7 | −0.3 (8) | C30—C22—N2—C36 | −96.8 (4) |
C5—C4—S1—C1 | −154.5 (4) | C30—C22—S2—C25 | −75.1 (3) |
C5—C6—C7—C8 | 1.3 (8) | C30—C35—C34—C33 | −1.4 (12) |
C6—C7—C8—C3 | −0.5 (7) | C35—C30—C31—C32 | 1.7 (8) |
C8—C3—C4—C5 | 2.2 (6) | C35—C34—C33—C32 | 1.8 (13) |
C8—C3—C4—S1 | 179.3 (3) | C34—C33—C32—C31 | −0.5 (11) |
C9—C1—N1—C2 | −77.0 (5) | C33—C32—C31—C30 | −1.3 (9) |
C9—C1—N1—C15 | 93.1 (4) | C31—C30—C35—C34 | −0.4 (9) |
C9—C1—S1—C4 | 76.4 (3) | C36—C37—C38—C39 | 0.2 (7) |
C9—C10—C11—C12 | 0.6 (10) | C37—C36—C41—C40 | 1.3 (6) |
C10—C9—C14—C13 | −0.6 (8) | C37—C36—N2—C22 | 46.0 (5) |
C10—C11—C12—C13 | −1.2 (12) | C37—C36—N2—C23 | −128.0 (4) |
C11—C12—C13—C14 | 0.9 (11) | C37—C38—C39—C40 | 0.6 (7) |
C12—C13—C14—C9 | 0.0 (9) | C37—C38—C39—C42 | −179.3 (5) |
C14—C9—C10—C11 | 0.3 (8) | C38—C39—C40—C41 | −0.5 (6) |
C15—C16—C17—C18 | −0.1 (7) | C38—C39—C42—F6A | −113 (2) |
C16—C15—C20—C19 | −1.9 (6) | C38—C39—C42—F5A | 9.7 (16) |
C16—C15—N1—C1 | −41.8 (5) | C38—C39—C42—F4A | 126.8 (15) |
C16—C15—N1—C2 | 128.6 (4) | C38—C39—C42—F4B | 79 (2) |
C16—C17—C18—C19 | −1.8 (7) | C38—C39—C42—F5B | −162.5 (19) |
C16—C17—C18—C21 | 175.8 (5) | C38—C39—C42—F6B | −47 (2) |
C17—C18—C19—C20 | 1.8 (6) | C39—C40—C41—C36 | −0.4 (6) |
C17—C18—C21—F1 | 51.4 (6) | C40—C39—C42—F6A | 67 (2) |
C17—C18—C21—F2 | 172.5 (5) | C40—C39—C42—F5A | −170.3 (15) |
C17—C18—C21—F3 | −66.5 (6) | C40—C39—C42—F4A | −53.1 (15) |
C18—C19—C20—C15 | 0.0 (6) | C40—C39—C42—F4B | −101 (2) |
C19—C18—C21—F1 | −131.0 (5) | C40—C39—C42—F5B | 17.5 (19) |
C19—C18—C21—F2 | −9.9 (7) | C40—C39—C42—F6B | 133 (2) |
C19—C18—C21—F3 | 111.2 (5) | C41—C36—C37—C38 | −1.2 (7) |
C20—C15—C16—C17 | 1.9 (7) | C41—C36—N2—C22 | −132.0 (4) |
C20—C15—N1—C1 | 136.4 (4) | C41—C36—N2—C23 | 54.0 (5) |
C20—C15—N1—C2 | −53.2 (5) | C42—C39—C40—C41 | 179.4 (4) |
C21—C18—C19—C20 | −175.7 (4) | N2—C22—C30—C35 | 163.7 (4) |
N1—C1—C9—C10 | −164.6 (4) | N2—C22—C30—C31 | −17.2 (6) |
N1—C1—C9—C14 | 13.5 (6) | N2—C22—S2—C25 | 53.7 (3) |
N1—C1—S1—C4 | −53.7 (3) | N2—C23—C24—C25 | 18.0 (5) |
N1—C2—C3—C4 | −19.7 (6) | N2—C23—C24—C29 | −165.2 (3) |
N1—C2—C3—C8 | 166.1 (3) | N2—C36—C37—C38 | −179.2 (4) |
N1—C15—C16—C17 | −179.9 (4) | N2—C36—C41—C40 | 179.3 (4) |
N1—C15—C20—C19 | 179.9 (4) | O2—C23—C24—C25 | −161.5 (4) |
O1—C2—C3—C4 | 160.7 (4) | O2—C23—C24—C29 | 15.4 (5) |
O1—C2—C3—C8 | −13.5 (6) | O2—C23—N2—C22 | −168.8 (4) |
O1—C2—N1—C1 | 167.0 (4) | O2—C23—N2—C36 | 4.9 (5) |
O1—C2—N1—C15 | −2.9 (6) | S2—C22—C30—C35 | −69.8 (5) |
S1—C1—C9—C10 | 67.3 (5) | S2—C22—C30—C31 | 109.3 (4) |
S1—C1—C9—C14 | −114.6 (4) | S2—C22—N2—C23 | −50.4 (4) |
S1—C1—N1—C2 | 51.9 (4) | S2—C22—N2—C36 | 135.8 (3) |
S1—C1—N1—C15 | −138.0 (3) | S2—C25—C26—C27 | 177.7 (4) |
S1—C4—C5—C6 | −178.6 (4) | C43—C44—C45—C46 | 0.4 (9) |
C22—C30—C35—C34 | 178.6 (6) | C44—C43—C48—C47 | 0.3 (8) |
C22—C30—C31—C32 | −177.3 (5) | C44—C45—C46—C47 | −0.1 (9) |
C23—C24—C25—C26 | 176.1 (4) | C45—C46—C47—C48 | −0.1 (8) |
C23—C24—C25—S2 | −1.5 (5) | C45—C46—C47—C49 | 179.3 (6) |
C23—C24—C29—C28 | −176.2 (4) | C46—C47—C48—C43 | 0.0 (8) |
C24—C23—N2—C22 | 11.7 (5) | C48—C43—C44—C45 | −0.5 (8) |
C24—C23—N2—C36 | −174.6 (3) | C49—C47—C48—C43 | −179.4 (6) |
Cg(X) = center of gravity of ring (X); D—H···CgX = angle of the D—H bond with the π plane |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O2 | 0.98 | 2.25 | 3.2053 (7) | 165 |
C22—H22···O1i | 0.98 | 2.34 | 3.3140 (7) | 171 |
C17—H17···Cg9 | 0.93 | 2.79 | 3.5916 (7) | 145 |
C38—H38···Cg9ii | 0.93 | 2.78 | 3.6009 (7) | 147 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1/2. |
2C20H14BrNOS·C7H8 | Dx = 1.485 Mg m−3 |
Mr = 884.72 | Melting point = 358–359 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.736 (2) Å | Cell parameters from 3326 reflections |
b = 9.3530 (15) Å | θ = 2.5–25.0° |
c = 27.259 (4) Å | µ = 2.20 mm−1 |
β = 99.560 (3)° | T = 298 K |
V = 3956.2 (10) Å3 | Block, colorless |
Z = 4 | 0.21 × 0.17 × 0.10 mm |
F(000) = 1800 |
Bruker CCD area-detector diffractometer | 2424 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.064 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | θmax = 28.3°, θmin = 2.5° |
Tmin = 0.103, Tmax = 0.901 | h = −20→20 |
18289 measured reflections | k = −12→12 |
4903 independent reflections | l = −36→36 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.79 | (Δ/σ)max < 0.001 |
4903 reflections | Δρmax = 0.73 e Å−3 |
266 parameters | Δρmin = −0.71 e Å−3 |
186 restraints |
Experimental. Absorption correction: SADABS was used for absorption correction. R(int) was 0.2680 before and 0.0355 after correction. The Ratio of minimum to maximum transmission is 0.1027. The λ/2 correction factor is 0.0015. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm. |
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 | Occ. (<1) | |
Br1 | 0.45074 (3) | 0.27453 (5) | 0.01191 (2) | 0.0874 (2) | |
C1 | 0.3189 (2) | −0.2500 (3) | −0.12554 (12) | 0.0471 (8) | |
H1 | 0.2798 | −0.2262 | −0.1023 | 0.057* | |
C2 | 0.4549 (2) | −0.1391 (3) | −0.14162 (11) | 0.0479 (8) | |
C3 | 0.4821 (2) | −0.2827 (3) | −0.15744 (12) | 0.0506 (8) | |
C4 | 0.4518 (2) | −0.4113 (3) | −0.14088 (11) | 0.0540 (9) | |
C5 | 0.4858 (3) | −0.5405 (4) | −0.15463 (15) | 0.0736 (12) | |
H5 | 0.4662 | −0.6269 | −0.1438 | 0.088* | |
C6 | 0.5487 (3) | −0.5386 (5) | −0.18431 (16) | 0.0840 (14) | |
H6 | 0.5723 | −0.6246 | −0.1927 | 0.101* | |
C7 | 0.5774 (3) | −0.4129 (5) | −0.20176 (15) | 0.0766 (12) | |
H7 | 0.6178 | −0.4141 | −0.2231 | 0.092* | |
C8 | 0.5453 (2) | −0.2859 (4) | −0.18817 (13) | 0.0613 (9) | |
H8 | 0.5657 | −0.2006 | −0.1994 | 0.074* | |
C9 | 0.2622 (2) | −0.2733 (3) | −0.17542 (11) | 0.0441 (7) | |
C10 | 0.2728 (2) | −0.1978 (4) | −0.21777 (12) | 0.0551 (9) | |
H10 | 0.3176 | −0.1322 | −0.2164 | 0.066* | |
C11 | 0.2169 (3) | −0.2193 (4) | −0.26239 (14) | 0.0650 (10) | |
H11 | 0.2250 | −0.1686 | −0.2906 | 0.078* | |
C12 | 0.1505 (3) | −0.3137 (4) | −0.26511 (14) | 0.0653 (10) | |
H12 | 0.1139 | −0.3288 | −0.2951 | 0.078* | |
C13 | 0.1381 (2) | −0.3865 (3) | −0.22331 (15) | 0.0646 (10) | |
H13 | 0.0915 | −0.4485 | −0.2247 | 0.078* | |
C14 | 0.1942 (2) | −0.3683 (3) | −0.17905 (13) | 0.0565 (9) | |
H14 | 0.1861 | −0.4209 | −0.1512 | 0.068* | |
C15 | 0.3547 (2) | 0.0010 (3) | −0.10271 (10) | 0.0444 (7) | |
C16 | 0.2748 (2) | 0.0582 (4) | −0.11998 (12) | 0.0605 (9) | |
H16 | 0.2388 | 0.0144 | −0.1462 | 0.073* | |
C17 | 0.2477 (3) | 0.1802 (4) | −0.09865 (14) | 0.0684 (11) | |
H17 | 0.1940 | 0.2192 | −0.1107 | 0.082* | |
C18 | 0.3005 (3) | 0.2443 (3) | −0.05941 (14) | 0.0602 (10) | |
H18 | 0.2825 | 0.3262 | −0.0447 | 0.072* | |
C19 | 0.3790 (2) | 0.1866 (3) | −0.04242 (12) | 0.0519 (8) | |
C20 | 0.4081 (2) | 0.0654 (3) | −0.06351 (11) | 0.0498 (8) | |
H20 | 0.4624 | 0.0280 | −0.0516 | 0.060* | |
N1 | 0.37987 (17) | −0.1309 (2) | −0.12306 (9) | 0.0436 (6) | |
O1 | 0.49900 (16) | −0.0328 (3) | −0.14536 (9) | 0.0642 (7) | |
S1 | 0.37419 (7) | −0.41236 (9) | −0.10170 (3) | 0.0632 (3) | |
C21 | 0.3612 (7) | −0.228 (2) | 0.0506 (4) | 0.146 (15) | 0.5 |
H21A | 0.4040 | −0.2957 | 0.0440 | 0.219* | 0.5 |
H21B | 0.3479 | −0.2455 | 0.0832 | 0.219* | 0.5 |
H21C | 0.3831 | −0.1330 | 0.0489 | 0.219* | 0.5 |
C22 | 0.2809 (6) | −0.2458 (12) | 0.0125 (3) | 0.135 (7) | 0.5 |
C23 | 0.2341 (8) | −0.1264 (10) | −0.0081 (4) | 0.123 (8) | 0.5 |
H23 | 0.2537 | −0.0351 | 0.0015 | 0.147* | 0.5 |
C24 | 0.1585 (7) | −0.1422 (11) | −0.0426 (4) | 0.145 (9) | 0.5 |
H24 | 0.1283 | −0.0618 | −0.0558 | 0.174* | 0.5 |
C25 | 0.1282 (5) | −0.2785 (13) | −0.0573 (3) | 0.160 (14) | 0.5 |
H25 | 0.0779 | −0.2893 | −0.0803 | 0.192* | 0.5 |
C26 | 0.1743 (6) | −0.3985 (10) | −0.0374 (3) | 0.086 (3) | 0.5 |
H26 | 0.1546 | −0.4896 | −0.0470 | 0.103* | 0.5 |
C27 | 0.2498 (6) | −0.3820 (10) | −0.0028 (3) | 0.105 (6) | 0.5 |
H27 | 0.2800 | −0.4626 | 0.0102 | 0.125* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0933 (4) | 0.0782 (3) | 0.0831 (3) | 0.0078 (2) | −0.0077 (2) | −0.0405 (2) |
C1 | 0.054 (2) | 0.0439 (17) | 0.0465 (18) | −0.0039 (14) | 0.0166 (15) | −0.0027 (13) |
C2 | 0.055 (2) | 0.0477 (18) | 0.0418 (17) | 0.0015 (16) | 0.0104 (15) | −0.0051 (13) |
C3 | 0.050 (2) | 0.0543 (18) | 0.0451 (18) | 0.0068 (15) | −0.0007 (15) | −0.0095 (14) |
C4 | 0.058 (2) | 0.0494 (18) | 0.0483 (18) | 0.0078 (16) | −0.0085 (15) | −0.0059 (14) |
C5 | 0.077 (3) | 0.050 (2) | 0.083 (3) | 0.0155 (19) | −0.017 (2) | −0.0109 (18) |
C6 | 0.076 (3) | 0.082 (3) | 0.086 (3) | 0.043 (3) | −0.010 (2) | −0.031 (2) |
C7 | 0.063 (3) | 0.099 (3) | 0.064 (2) | 0.026 (2) | −0.0003 (19) | −0.021 (2) |
C8 | 0.050 (2) | 0.080 (2) | 0.053 (2) | 0.0138 (19) | 0.0033 (17) | −0.0137 (17) |
C9 | 0.050 (2) | 0.0359 (14) | 0.0486 (18) | 0.0026 (14) | 0.0144 (15) | −0.0056 (12) |
C10 | 0.056 (2) | 0.0550 (19) | 0.055 (2) | −0.0074 (16) | 0.0098 (17) | −0.0003 (15) |
C11 | 0.070 (3) | 0.070 (2) | 0.054 (2) | 0.003 (2) | 0.0094 (19) | −0.0010 (17) |
C12 | 0.067 (3) | 0.056 (2) | 0.067 (2) | 0.009 (2) | −0.0057 (19) | −0.0172 (18) |
C13 | 0.056 (3) | 0.0447 (18) | 0.091 (3) | −0.0053 (17) | 0.004 (2) | −0.0168 (19) |
C14 | 0.058 (2) | 0.0423 (17) | 0.070 (2) | −0.0031 (16) | 0.0157 (18) | −0.0022 (15) |
C15 | 0.056 (2) | 0.0394 (15) | 0.0404 (16) | −0.0004 (14) | 0.0144 (15) | −0.0006 (12) |
C16 | 0.062 (2) | 0.062 (2) | 0.054 (2) | 0.0100 (18) | −0.0033 (17) | −0.0125 (16) |
C17 | 0.065 (3) | 0.066 (2) | 0.069 (2) | 0.024 (2) | −0.0027 (19) | −0.0134 (19) |
C18 | 0.075 (3) | 0.0435 (18) | 0.064 (2) | 0.0102 (17) | 0.015 (2) | −0.0054 (15) |
C19 | 0.063 (2) | 0.0442 (16) | 0.0478 (18) | 0.0006 (16) | 0.0085 (16) | −0.0081 (14) |
C20 | 0.054 (2) | 0.0458 (17) | 0.0496 (18) | 0.0016 (15) | 0.0098 (15) | −0.0043 (14) |
N1 | 0.0467 (17) | 0.0403 (13) | 0.0457 (14) | −0.0042 (11) | 0.0132 (12) | −0.0079 (11) |
O1 | 0.0639 (17) | 0.0552 (14) | 0.0797 (16) | −0.0133 (12) | 0.0304 (13) | −0.0105 (12) |
S1 | 0.0802 (7) | 0.0477 (5) | 0.0597 (5) | −0.0038 (4) | 0.0061 (5) | 0.0101 (4) |
C21 | 0.062 (11) | 0.31 (5) | 0.074 (10) | −0.006 (17) | 0.029 (9) | 0.029 (15) |
C22 | 0.131 (17) | 0.196 (15) | 0.104 (13) | −0.034 (15) | 0.096 (13) | −0.052 (12) |
C23 | 0.147 (16) | 0.109 (14) | 0.143 (13) | −0.016 (13) | 0.118 (12) | −0.049 (13) |
C24 | 0.19 (2) | 0.097 (10) | 0.18 (2) | 0.028 (11) | 0.128 (17) | 0.041 (11) |
C25 | 0.120 (17) | 0.26 (4) | 0.123 (15) | −0.085 (18) | 0.076 (12) | −0.080 (18) |
C26 | 0.088 (8) | 0.094 (7) | 0.084 (7) | 0.004 (6) | 0.040 (6) | 0.014 (6) |
C27 | 0.174 (18) | 0.056 (8) | 0.106 (10) | 0.002 (9) | 0.088 (11) | 0.002 (6) |
Br1—C19 | 1.895 (3) | C13—C14 | 1.383 (5) |
C1—H1 | 0.9800 | C14—H14 | 0.9300 |
C1—C9 | 1.513 (5) | C15—C16 | 1.376 (4) |
C1—N1 | 1.464 (4) | C15—C20 | 1.382 (4) |
C1—S1 | 1.815 (3) | C15—N1 | 1.435 (4) |
C2—C3 | 1.494 (4) | C16—H16 | 0.9300 |
C2—N1 | 1.362 (4) | C16—C17 | 1.380 (5) |
C2—O1 | 1.227 (4) | C17—H17 | 0.9300 |
C3—C4 | 1.396 (5) | C17—C18 | 1.377 (5) |
C3—C8 | 1.404 (5) | C18—H18 | 0.9300 |
C4—C5 | 1.398 (5) | C18—C19 | 1.357 (5) |
C4—S1 | 1.750 (4) | C19—C20 | 1.384 (4) |
C5—H5 | 0.9300 | C20—H20 | 0.9300 |
C5—C6 | 1.379 (6) | C21—H21A | 0.9600 |
C6—H6 | 0.9300 | C21—H21B | 0.9600 |
C6—C7 | 1.372 (6) | C21—H21C | 0.9600 |
C7—H7 | 0.9297 | C21—C22 | 1.5069 |
C7—C8 | 1.365 (5) | C22—C23 | 1.4022 |
C8—H8 | 0.9300 | C22—C27 | 1.4024 |
C9—C10 | 1.387 (5) | C23—H23 | 0.9300 |
C9—C14 | 1.382 (4) | C23—C24 | 1.3963 |
C10—H10 | 0.9300 | C24—H24 | 0.9300 |
C10—C11 | 1.392 (5) | C24—C25 | 1.3964 |
C11—H11 | 0.9300 | C25—H25 | 0.9300 |
C11—C12 | 1.361 (5) | C25—C26 | 1.3966 |
C12—H12 | 0.9300 | C26—H26 | 0.9300 |
C12—C13 | 1.369 (5) | C26—C27 | 1.3963 |
C13—H13 | 0.9300 | C27—H27 | 0.9300 |
C9—C1—H1 | 105.9 | C16—C15—N1 | 119.8 (3) |
C9—C1—S1 | 112.2 (2) | C20—C15—N1 | 120.1 (3) |
N1—C1—H1 | 105.9 | C15—C16—H16 | 119.8 |
N1—C1—C9 | 115.8 (2) | C15—C16—C17 | 120.4 (3) |
N1—C1—S1 | 110.4 (2) | C17—C16—H16 | 119.8 |
S1—C1—H1 | 105.9 | C16—C17—H17 | 120.0 |
N1—C2—C3 | 117.7 (3) | C18—C17—C16 | 119.9 (3) |
O1—C2—C3 | 120.8 (3) | C18—C17—H17 | 120.0 |
O1—C2—N1 | 121.5 (3) | C17—C18—H18 | 120.4 |
C4—C3—C2 | 123.5 (3) | C19—C18—C17 | 119.3 (3) |
C4—C3—C8 | 119.3 (3) | C19—C18—H18 | 120.4 |
C8—C3—C2 | 117.1 (3) | C18—C19—Br1 | 119.0 (2) |
C3—C4—C5 | 119.4 (4) | C18—C19—C20 | 122.0 (3) |
C3—C4—S1 | 120.8 (2) | C20—C19—Br1 | 119.0 (3) |
C5—C4—S1 | 119.7 (3) | C15—C20—C19 | 118.5 (3) |
C4—C5—H5 | 120.3 | C15—C20—H20 | 120.8 |
C6—C5—C4 | 119.4 (4) | C19—C20—H20 | 120.8 |
C6—C5—H5 | 120.3 | C2—N1—C1 | 122.8 (2) |
C5—C6—H6 | 119.2 | C2—N1—C15 | 120.2 (2) |
C7—C6—C5 | 121.6 (4) | C15—N1—C1 | 116.9 (2) |
C7—C6—H6 | 119.2 | C4—S1—C1 | 96.77 (15) |
C6—C7—H7 | 120.3 | H21A—C21—H21B | 109.5 |
C8—C7—C6 | 119.6 (4) | H21A—C21—H21C | 109.5 |
C8—C7—H7 | 120.1 | H21B—C21—H21C | 109.5 |
C3—C8—H8 | 119.6 | C22—C21—H21A | 109.5 |
C7—C8—C3 | 120.7 (4) | C22—C21—H21B | 109.5 |
C7—C8—H8 | 119.6 | C22—C21—H21C | 109.5 |
C10—C9—C1 | 122.7 (3) | C23—C22—C21 | 121.0 |
C14—C9—C1 | 119.4 (3) | C23—C22—C27 | 118.1 |
C14—C9—C10 | 117.8 (3) | C27—C22—C21 | 120.9 |
C9—C10—H10 | 119.7 | C22—C23—H23 | 119.4 |
C9—C10—C11 | 120.5 (3) | C24—C23—C22 | 121.1 |
C11—C10—H10 | 119.7 | C24—C23—H23 | 119.4 |
C10—C11—H11 | 119.7 | C23—C24—H24 | 119.9 |
C12—C11—C10 | 120.6 (4) | C23—C24—C25 | 120.1 |
C12—C11—H11 | 119.7 | C25—C24—H24 | 119.9 |
C11—C12—H12 | 120.3 | C24—C25—H25 | 120.3 |
C11—C12—C13 | 119.5 (3) | C24—C25—C26 | 119.4 |
C13—C12—H12 | 120.3 | C26—C25—H25 | 120.3 |
C12—C13—H13 | 119.8 | C25—C26—H26 | 119.9 |
C12—C13—C14 | 120.4 (3) | C27—C26—C25 | 120.1 |
C14—C13—H13 | 119.8 | C27—C26—H26 | 119.9 |
C9—C14—C13 | 121.1 (3) | C22—C27—H27 | 119.5 |
C9—C14—H14 | 119.4 | C26—C27—C22 | 121.1 |
C13—C14—H14 | 119.4 | C26—C27—H27 | 119.5 |
C16—C15—C20 | 119.9 (3) | ||
Br1—C19—C20—C15 | 179.2 (2) | C17—C18—C19—Br1 | −179.5 (3) |
C1—C9—C10—C11 | −177.6 (3) | C17—C18—C19—C20 | 0.4 (6) |
C1—C9—C14—C13 | 176.3 (3) | C18—C19—C20—C15 | −0.7 (5) |
C2—C3—C4—C5 | −175.0 (3) | C20—C15—C16—C17 | 0.5 (5) |
C2—C3—C4—S1 | 3.0 (5) | C20—C15—N1—C1 | 125.6 (3) |
C2—C3—C8—C7 | 176.0 (3) | C20—C15—N1—C2 | −58.2 (4) |
C3—C2—N1—C1 | −10.2 (4) | N1—C1—C9—C10 | 6.7 (4) |
C3—C2—N1—C15 | 173.8 (3) | N1—C1—C9—C14 | −170.0 (3) |
C3—C4—C5—C6 | 0.0 (5) | N1—C1—S1—C4 | −54.9 (2) |
C3—C4—S1—C1 | 31.4 (3) | N1—C2—C3—C4 | −20.5 (5) |
C4—C3—C8—C7 | −0.2 (5) | N1—C2—C3—C8 | 163.5 (3) |
C4—C5—C6—C7 | −1.6 (6) | N1—C15—C16—C17 | 176.0 (3) |
C5—C4—S1—C1 | −150.5 (3) | N1—C15—C20—C19 | −175.2 (3) |
C5—C6—C7—C8 | 2.3 (6) | O1—C2—C3—C4 | 159.5 (3) |
C6—C7—C8—C3 | −1.4 (6) | O1—C2—C3—C8 | −16.5 (5) |
C8—C3—C4—C5 | 0.9 (5) | O1—C2—N1—C1 | 169.7 (3) |
C8—C3—C4—S1 | 179.0 (2) | O1—C2—N1—C15 | −6.2 (4) |
C9—C1—N1—C2 | −77.8 (4) | S1—C1—C9—C10 | −121.2 (3) |
C9—C1—N1—C15 | 98.2 (3) | S1—C1—C9—C14 | 62.0 (4) |
C9—C1—S1—C4 | 75.8 (3) | S1—C1—N1—C2 | 51.0 (3) |
C9—C10—C11—C12 | 0.6 (5) | S1—C1—N1—C15 | −132.9 (2) |
C10—C9—C14—C13 | −0.6 (5) | S1—C4—C5—C6 | −178.1 (3) |
C10—C11—C12—C13 | 1.0 (6) | C21—C22—C23—C24 | −178.5 |
C11—C12—C13—C14 | −2.4 (5) | C21—C22—C27—C26 | 178.5 |
C12—C13—C14—C9 | 2.2 (5) | C22—C23—C24—C25 | −0.1 |
C14—C9—C10—C11 | −0.8 (5) | C23—C22—C27—C26 | −0.3 |
C15—C16—C17—C18 | −0.9 (6) | C23—C24—C25—C26 | −0.1 |
C16—C15—C20—C19 | 0.3 (5) | C24—C25—C26—C27 | 0.1 |
C16—C15—N1—C1 | −49.8 (4) | C25—C26—C27—C22 | 0.1 |
C16—C15—N1—C2 | 126.4 (3) | C27—C22—C23—C24 | 0.3 |
C16—C17—C18—C19 | 0.4 (6) |
Cg(X) = center of gravity of ring (X); D—H···Cg(X) = angle of the D—H bond with the π plane |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cg5 | 0.98 | 2.66 | 3.5802 (6) | 156 |
C6—H6···Cg3i | 0.93 | 2.83 | 3.6823 (6) | 153 |
Symmetry code: (i) −x−1, −y, −z. |
Acknowledgements
We thank SP Controls, Inc. for the summer support of DJC, Euticals for the gift of T3P in 2-methyltetrahydrofuran, Penn State Schuylkill for financial support, and NSF funding (CHEM-0131112) for the X-ray diffractometer.
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