research communications
Crystal structures of 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene
aFaculty of Chemistry, VNU University of Science, Vietnam National University, Hanoi, 19 Le Thanh Tong, Ha Noi, Vietnam
*Correspondence e-mail: thaithanhthubui@gmail.com
Two thiochromene compounds containing Br and F atoms, namely 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene (C17H13BrFNO3S, A) and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene (C16H11BrFNO3S, B), were prepared via the condensation reaction between 2-mercaptobenzaldehyde and nitrostyrene derivatives. In both compounds, the thiochromene plane is almost perpendicular to the phenyl ring. In the structure of A, molecules are assembled via π–π stacking and C—H⋯O and C—F⋯π interactions. In the crystal packing of B, molecules are linked by C—H⋯F, C—H⋯O, C—H⋯π and π–π interactions.
Keywords: crystal structure; thiochromene; hydrogen bonding; π–π stacking.
1. Chemical context
2H-Chromenes (or 2H-benzopyrans) are heterocyclic compounds found in many natural plants. This class of molecules shows a wide variety of biological activities, such as anticancer, anti-inflammation and anti-HIV (Horton et al., 2003). Recently, we have shown that 3-nitro-2H-chromene can act as a selective mTOR/Pi3K inhibitor, which can lead to a new compound to treat breast cancer (Fouqué et al., 2015). Interestingly, we observed that thiochromene derivatives, where the O atom is replaced by an S atom, can increase significantly the biological activity of these compounds. With the goal in mind to synthesize a chemical library of thiochromene compounds (Nguyen et al., 2016), we have now successfully prepared 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene (A) and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene (B). determination can help to understand the role of halogenated substituents in the biological activity of these compounds.
2. Structural commentary
Compound (A) crystallizes in the triclinic P, while compound (B) crystallizes in the P21/c, both with one molecule in the (Figs. 1 and 2). In both compounds, the conformation of the thiochromene ring is similar. In A, the thiochromene ring makes an angle of 89.3 (2)° with phenyl ring C1–C6, while in B, this angle is 86.94 (8)°, which indicates that the 2-bromo-5-fluorophenyl ring is roughly perpendicular to the thiochromene plane. Both 2H-thiopyran rings have a screw-boat conformation, with atom C7 having the largest deviation from the best plane through atoms S1/C7–C11 [puckering parameters Q = 0.388 (4) Å, θ = 119.6 (7)° and φ = 202.2 (9)° for A, and Q = 0.5111 (18) Å, θ = 118.2 (2)° and φ = 208.1 (3)° for B]. The C—S bond lengths are almost equal [C7—S1 = 1.828 (4) Å and C11—S1 = 1.8307 (19) Å for A, and 1.758 (5) and 1.7574 (19) Å for B, respectively]. The C11—S1—C7 bond angle is 102.5 (2)° in A and 100.47 (9)° in B. The N—O bond lengths in compound B [1.232 (2) and 1.221 (2) Å] are slightly longer than those in compound A [both 1.219 (5) Å]. The nitro group is situated in the thiochromene plane, as illustrated by the torsion angle O2—N8—C8—C9 of 1.3 (7)° in A and 9.5 (3)° in B.
3. Supramolecular features
In the crystal of A, molecules form inversion dimers via C—H⋯O hydrogen bonds (Table 1 and Fig. 3) and π–π interactions [Cg3⋯Cg3i = 3.646 (3) Å; symmetry code: (i) −x, −y + 2, −z; Cg3 is the centroid of the C10–C15 ring]. Neighbouring dimers interact through C—F⋯π and short Br1⋯H5ii interactions [F4⋯Cg3ii = 3.328 (4) Å and Br1⋯H5iii = 2.96 Å; symmetry codes: (ii) −x, −y + 1, −z + 1; (iii) x + 1, y, z].
In the crystal of compound B, two molecules form dimers through C—H⋯F hydrogen bonds (Table 2 and Fig. 4). These dimers form chains running in the c direction through π–π interactions [Cg2⋯Cg2i = 3.8458 (13) Å; symmetry code: (i) −x + 2, −y + 1, −z + 1; Cg2 is the centroid of the C1–C6 ring]. Parallel chains interact via C—H⋯O and C—H⋯π interactions.
4. Database survey
The Cambridge Structural Database (CSD, Version 5.40, update of May 2019; Groom et al., 2016) contains seven phenyl-2H-thiochromene derivatives, of which three contain halogen atoms [CSD refcodes IFOZIO (Choudhury & Mukherjee, 2013), QAPSAE (Simlandy & Mukherjee, 2017) and WAPCUO (Sangeetha & Sekar, 2017)] and only one structure contains a nitro substituent on the 2H-thiochromene ring (NOGDIZ; Le et al., 2019). In all seven structures, the phenyl ring is roughly perpendicular to the thiochromene plane, with dihedral angles between 87.73 and 98.89°. Four of the seven structures display intermolecular interactions between the S atom and a C—H bond. However, in the two structures presented here, this type of interaction has not been observed.
5. Synthesis and crystallization
To a round-bottomed flask was added 2-mercaptobenzaldehyde (1 equiv.), nitrostyrene (1 equiv.) and K2CO3 (1 equiv.) in toluene and the reaction mixture was stirred at room temperature for 2 h. After completion of the reaction, the solvent was evaporated under reduced pressure and the crude product was purified by flash on silica gel (yield 90%). Crystals suitable for single-crystal X-ray diffraction data collection were obtained by slow evaporation from an ethanol solution.
6. Refinement
Crystal data, data collection and structure . All H atoms bonded to C atoms were placed at calculated positions, with C—H = 0.93–0.98 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C) for Csp2—H and Uiso(H) = 1.5Ueq(C) for Csp3—H. A rotating-group model was applied for methyl-group C17 in A and C16 in B.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989019014178/vm2223sup1.cif
contains datablocks A, B, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Asup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Bsup5.cml
Structure factors: contains datablock A. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Asup8.hkl
Structure factors: contains datablock B. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Bsup9.hkl
For both structures, data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C17H13BrFNO3S | Z = 2 |
Mr = 410.25 | F(000) = 412 |
Triclinic, P1 | Dx = 1.590 Mg m−3 |
a = 7.6695 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6867 (18) Å | Cell parameters from 5933 reflections |
c = 12.2767 (19) Å | θ = 3.0–25.6° |
α = 64.686 (4)° | µ = 2.55 mm−1 |
β = 80.760 (4)° | T = 273 K |
γ = 70.395 (4)° | Triangular-prism, clear light yellow |
V = 856.7 (2) Å3 | 0.25 × 0.2 × 0.15 mm |
Bruker D8 Quest CMOS diffractometer | 2291 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.7°, θmin = 3.0° |
Tmin = 0.621, Tmax = 0.745 | h = −9→9 |
12684 measured reflections | k = −13→13 |
3255 independent reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0419P)2 + 2.0237P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3255 reflections | Δρmax = 0.53 e Å−3 |
218 parameters | Δρmin = −0.49 e Å−3 |
0 restraints |
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 | ||
Br1 | 0.78831 (7) | 0.45042 (7) | 0.29672 (6) | 0.0676 (2) | |
S1 | 0.34737 (16) | 0.76031 (13) | 0.17001 (11) | 0.0459 (3) | |
F4 | 0.1093 (5) | 0.3152 (4) | 0.5616 (3) | 0.0878 (11) | |
O1 | 0.4800 (5) | 0.3584 (4) | 0.1158 (3) | 0.0627 (10) | |
N8 | 0.3239 (6) | 0.4388 (5) | 0.0863 (4) | 0.0514 (10) | |
O3 | 0.1347 (6) | 0.9891 (4) | 0.2321 (4) | 0.0800 (12) | |
C6 | 0.4041 (5) | 0.4707 (4) | 0.3176 (4) | 0.0317 (9) | |
C7 | 0.3916 (5) | 0.5738 (5) | 0.1873 (4) | 0.0344 (10) | |
H7 | 0.5137 | 0.5464 | 0.1505 | 0.041* | |
O2 | 0.2238 (6) | 0.4176 (5) | 0.0326 (4) | 0.0877 (14) | |
C1 | 0.5698 (6) | 0.4073 (5) | 0.3787 (4) | 0.0398 (10) | |
C5 | 0.2496 (6) | 0.4375 (5) | 0.3831 (4) | 0.0430 (11) | |
H5 | 0.1353 | 0.4785 | 0.3463 | 0.052* | |
C8 | 0.2567 (6) | 0.5648 (5) | 0.1183 (4) | 0.0394 (11) | |
C9 | 0.0857 (6) | 0.6514 (5) | 0.0895 (4) | 0.0441 (11) | |
H9 | 0.0162 | 0.6300 | 0.0480 | 0.053* | |
C10 | 0.0005 (6) | 0.7756 (5) | 0.1180 (4) | 0.0449 (12) | |
C11 | 0.1047 (6) | 0.8283 (5) | 0.1624 (4) | 0.0440 (11) | |
C2 | 0.5820 (7) | 0.3155 (5) | 0.4989 (5) | 0.0540 (13) | |
H2 | 0.6945 | 0.2760 | 0.5376 | 0.065* | |
C4 | 0.2649 (7) | 0.3447 (6) | 0.5014 (4) | 0.0538 (13) | |
C12 | 0.0194 (8) | 0.9462 (6) | 0.1916 (5) | 0.0588 (14) | |
C3 | 0.4268 (8) | 0.2827 (6) | 0.5611 (5) | 0.0593 (14) | |
H3 | 0.4323 | 0.2196 | 0.6420 | 0.071* | |
C15 | −0.1906 (7) | 0.8446 (6) | 0.1038 (5) | 0.0612 (15) | |
H15 | −0.2617 | 0.8100 | 0.0751 | 0.073* | |
C13 | −0.1723 (9) | 1.0141 (6) | 0.1749 (6) | 0.0758 (19) | |
H13 | −0.2306 | 1.0946 | 0.1932 | 0.091* | |
C14 | −0.2721 (8) | 0.9611 (7) | 0.1315 (5) | 0.0757 (19) | |
H14 | −0.3987 | 1.0062 | 0.1209 | 0.091* | |
C16 | 0.0603 (12) | 1.1016 (8) | 0.2740 (8) | 0.108 (3) | |
H16A | −0.0355 | 1.0799 | 0.3348 | 0.129* | |
H16B | 0.0066 | 1.1929 | 0.2080 | 0.129* | |
C17 | 0.2145 (15) | 1.1110 (9) | 0.3261 (10) | 0.140 (4) | |
H17A | 0.3043 | 1.1391 | 0.2639 | 0.211* | |
H17B | 0.2717 | 1.0182 | 0.3877 | 0.211* | |
H17C | 0.1673 | 1.1819 | 0.3604 | 0.211* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0326 (3) | 0.0840 (5) | 0.0826 (4) | −0.0170 (3) | −0.0096 (2) | −0.0277 (3) |
S1 | 0.0434 (6) | 0.0424 (7) | 0.0506 (7) | −0.0164 (5) | −0.0098 (5) | −0.0116 (6) |
F4 | 0.084 (2) | 0.116 (3) | 0.0506 (19) | −0.054 (2) | 0.0178 (17) | −0.0102 (19) |
O1 | 0.056 (2) | 0.070 (3) | 0.071 (3) | −0.014 (2) | −0.0018 (19) | −0.040 (2) |
N8 | 0.057 (3) | 0.069 (3) | 0.045 (2) | −0.029 (2) | 0.004 (2) | −0.031 (2) |
O3 | 0.094 (3) | 0.049 (2) | 0.096 (3) | −0.013 (2) | 0.003 (2) | −0.036 (2) |
C6 | 0.031 (2) | 0.035 (2) | 0.034 (2) | −0.0095 (18) | −0.0047 (17) | −0.0171 (19) |
C7 | 0.029 (2) | 0.046 (3) | 0.034 (2) | −0.0144 (19) | 0.0037 (17) | −0.020 (2) |
O2 | 0.078 (3) | 0.129 (4) | 0.105 (3) | −0.037 (3) | −0.012 (2) | −0.083 (3) |
C1 | 0.038 (2) | 0.034 (2) | 0.047 (3) | −0.005 (2) | −0.007 (2) | −0.018 (2) |
C5 | 0.038 (2) | 0.052 (3) | 0.040 (3) | −0.016 (2) | −0.002 (2) | −0.017 (2) |
C8 | 0.037 (2) | 0.058 (3) | 0.029 (2) | −0.022 (2) | 0.0029 (18) | −0.019 (2) |
C9 | 0.039 (2) | 0.064 (3) | 0.030 (2) | −0.026 (2) | −0.0020 (19) | −0.011 (2) |
C10 | 0.035 (2) | 0.051 (3) | 0.034 (3) | −0.013 (2) | −0.0046 (19) | −0.002 (2) |
C11 | 0.043 (3) | 0.039 (3) | 0.031 (2) | −0.008 (2) | 0.0030 (19) | −0.002 (2) |
C2 | 0.058 (3) | 0.046 (3) | 0.050 (3) | −0.004 (3) | −0.023 (3) | −0.013 (2) |
C4 | 0.064 (3) | 0.062 (3) | 0.040 (3) | −0.030 (3) | 0.007 (2) | −0.018 (3) |
C12 | 0.067 (4) | 0.039 (3) | 0.054 (3) | −0.013 (3) | 0.005 (3) | −0.008 (3) |
C3 | 0.083 (4) | 0.051 (3) | 0.035 (3) | −0.021 (3) | −0.012 (3) | −0.006 (2) |
C15 | 0.043 (3) | 0.061 (4) | 0.050 (3) | −0.011 (3) | −0.003 (2) | 0.002 (3) |
C13 | 0.069 (4) | 0.046 (3) | 0.069 (4) | 0.005 (3) | 0.019 (3) | −0.007 (3) |
C14 | 0.048 (3) | 0.067 (4) | 0.062 (4) | −0.003 (3) | 0.006 (3) | 0.006 (3) |
C16 | 0.130 (7) | 0.070 (5) | 0.128 (7) | −0.011 (5) | −0.009 (5) | −0.057 (5) |
C17 | 0.187 (10) | 0.072 (5) | 0.179 (10) | −0.016 (6) | −0.027 (8) | −0.075 (6) |
Br1—C1 | 1.901 (4) | C10—C11 | 1.400 (7) |
S1—C7 | 1.828 (4) | C10—C15 | 1.403 (7) |
S1—C11 | 1.758 (5) | C11—C12 | 1.379 (7) |
F4—C4 | 1.356 (6) | C2—H2 | 0.9300 |
O1—N8 | 1.219 (5) | C2—C3 | 1.372 (7) |
N8—O2 | 1.219 (5) | C4—C3 | 1.357 (7) |
N8—C8 | 1.468 (6) | C12—C13 | 1.408 (8) |
O3—C12 | 1.360 (7) | C3—H3 | 0.9300 |
O3—C16 | 1.418 (8) | C15—H15 | 0.9300 |
C6—C7 | 1.501 (6) | C15—C14 | 1.353 (9) |
C6—C1 | 1.389 (6) | C13—H13 | 0.9300 |
C6—C5 | 1.381 (6) | C13—C14 | 1.367 (9) |
C7—H7 | 0.9800 | C14—H14 | 0.9300 |
C7—C8 | 1.488 (6) | C16—H16A | 0.9700 |
C1—C2 | 1.376 (7) | C16—H16B | 0.9700 |
C5—H5 | 0.9300 | C16—C17 | 1.481 (11) |
C5—C4 | 1.361 (6) | C17—H17A | 0.9600 |
C8—C9 | 1.325 (6) | C17—H17B | 0.9600 |
C9—H9 | 0.9300 | C17—H17C | 0.9600 |
C9—C10 | 1.433 (7) | ||
C11—S1—C7 | 102.5 (2) | C3—C2—C1 | 119.4 (5) |
O1—N8—C8 | 117.8 (4) | C3—C2—H2 | 120.3 |
O2—N8—O1 | 122.5 (5) | F4—C4—C5 | 117.7 (5) |
O2—N8—C8 | 119.8 (4) | F4—C4—C3 | 119.2 (5) |
C12—O3—C16 | 119.7 (5) | C3—C4—C5 | 123.1 (5) |
C1—C6—C7 | 121.8 (4) | O3—C12—C11 | 114.8 (5) |
C5—C6—C7 | 121.3 (4) | O3—C12—C13 | 125.5 (6) |
C5—C6—C1 | 117.0 (4) | C11—C12—C13 | 119.6 (6) |
S1—C7—H7 | 106.6 | C2—C3—H3 | 120.9 |
C6—C7—S1 | 111.5 (3) | C4—C3—C2 | 118.2 (5) |
C6—C7—H7 | 106.6 | C4—C3—H3 | 120.9 |
C8—C7—S1 | 111.0 (3) | C10—C15—H15 | 119.8 |
C8—C7—C6 | 114.2 (3) | C14—C15—C10 | 120.4 (6) |
C8—C7—H7 | 106.6 | C14—C15—H15 | 119.8 |
C6—C1—Br1 | 119.9 (3) | C12—C13—H13 | 120.2 |
C2—C1—Br1 | 117.9 (3) | C14—C13—C12 | 119.6 (6) |
C2—C1—C6 | 122.3 (4) | C14—C13—H13 | 120.2 |
C6—C5—H5 | 120.0 | C15—C14—C13 | 121.4 (6) |
C4—C5—C6 | 119.9 (4) | C15—C14—H14 | 119.3 |
C4—C5—H5 | 120.0 | C13—C14—H14 | 119.3 |
N8—C8—C7 | 113.7 (4) | O3—C16—H16A | 110.3 |
C9—C8—N8 | 118.5 (4) | O3—C16—H16B | 110.3 |
C9—C8—C7 | 127.7 (4) | O3—C16—C17 | 107.3 (7) |
C8—C9—H9 | 117.8 | H16A—C16—H16B | 108.5 |
C8—C9—C10 | 124.5 (4) | C17—C16—H16A | 110.3 |
C10—C9—H9 | 117.8 | C17—C16—H16B | 110.3 |
C11—C10—C9 | 120.9 (4) | C16—C17—H17A | 109.5 |
C11—C10—C15 | 119.0 (5) | C16—C17—H17B | 109.5 |
C15—C10—C9 | 120.1 (5) | C16—C17—H17C | 109.5 |
C10—C11—S1 | 122.3 (4) | H17A—C17—H17B | 109.5 |
C12—C11—S1 | 117.5 (4) | H17A—C17—H17C | 109.5 |
C12—C11—C10 | 120.0 (5) | H17B—C17—H17C | 109.5 |
C1—C2—H2 | 120.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O2i | 0.93 | 2.50 | 3.419 (7) | 168 |
Symmetry code: (i) −x, −y+1, −z. |
C16H11BrFNO3S | F(000) = 792 |
Mr = 396.23 | Dx = 1.749 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6231 (4) Å | Cell parameters from 9945 reflections |
b = 17.3484 (8) Å | θ = 3.0–28.3° |
c = 11.8345 (6) Å | µ = 2.90 mm−1 |
β = 106.016 (2)° | T = 273 K |
V = 1504.35 (13) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.22 × 0.11 mm |
Bruker D8 Quest CMOS diffractometer | 3018 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 28.4°, θmin = 3.0° |
Tmin = 0.599, Tmax = 0.746 | h = −10→10 |
31660 measured reflections | k = −23→23 |
3745 independent reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0274P)2 + 0.9845P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3745 reflections | Δρmax = 0.52 e Å−3 |
209 parameters | Δρmin = −0.49 e Å−3 |
0 restraints |
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 | ||
Br1 | 0.57090 (3) | 0.36398 (2) | 0.38157 (2) | 0.04708 (9) | |
S1 | 0.52686 (6) | 0.31114 (3) | 0.66185 (4) | 0.03212 (11) | |
F4 | 1.0275 (2) | 0.57875 (8) | 0.73645 (12) | 0.0538 (4) | |
O3 | 0.2529 (2) | 0.42250 (10) | 0.96347 (13) | 0.0458 (4) | |
O2 | 1.1678 (2) | 0.23148 (10) | 0.82659 (17) | 0.0550 (4) | |
O1 | 1.0798 (2) | 0.26267 (11) | 0.64265 (15) | 0.0545 (4) | |
N8 | 1.0577 (2) | 0.26017 (10) | 0.74190 (18) | 0.0383 (4) | |
C6 | 0.7901 (2) | 0.40495 (10) | 0.61148 (16) | 0.0265 (4) | |
C1 | 0.7106 (3) | 0.43164 (11) | 0.49777 (16) | 0.0306 (4) | |
C8 | 0.8921 (3) | 0.29553 (11) | 0.75735 (17) | 0.0307 (4) | |
C7 | 0.7581 (3) | 0.32337 (11) | 0.64724 (16) | 0.0289 (4) | |
H7 | 0.7692 | 0.2893 | 0.5835 | 0.035* | |
C11 | 0.5550 (3) | 0.34811 (11) | 0.80401 (16) | 0.0288 (4) | |
C12 | 0.4044 (3) | 0.37801 (11) | 0.83133 (17) | 0.0325 (4) | |
H12 | 0.2966 | 0.3854 | 0.7721 | 0.039* | |
C10 | 0.7218 (3) | 0.33978 (11) | 0.89180 (17) | 0.0311 (4) | |
C5 | 0.8972 (3) | 0.45668 (11) | 0.69165 (16) | 0.0300 (4) | |
H5 | 0.9539 | 0.4411 | 0.7682 | 0.036* | |
C2 | 0.7313 (3) | 0.50680 (13) | 0.46588 (18) | 0.0375 (5) | |
H2 | 0.6742 | 0.5232 | 0.3898 | 0.045* | |
C9 | 0.8784 (3) | 0.30534 (11) | 0.86622 (17) | 0.0338 (4) | |
H9 | 0.9746 | 0.2892 | 0.9287 | 0.041* | |
C4 | 0.9184 (3) | 0.53081 (12) | 0.65674 (18) | 0.0349 (4) | |
C14 | 0.5759 (3) | 0.39037 (13) | 1.03475 (18) | 0.0385 (5) | |
H14 | 0.5829 | 0.4043 | 1.1118 | 0.046* | |
C15 | 0.7271 (3) | 0.36263 (12) | 1.00596 (17) | 0.0361 (4) | |
H15 | 0.8368 | 0.3589 | 1.0646 | 0.043* | |
C13 | 0.4121 (3) | 0.39734 (12) | 0.94672 (18) | 0.0347 (4) | |
C3 | 0.8361 (3) | 0.55789 (12) | 0.54603 (19) | 0.0386 (5) | |
H3 | 0.8503 | 0.6088 | 0.5256 | 0.046* | |
C16 | 0.2464 (4) | 0.43592 (16) | 1.0811 (2) | 0.0534 (6) | |
H16A | 0.1254 | 0.4515 | 1.0807 | 0.080* | |
H16B | 0.3313 | 0.4759 | 1.1157 | 0.080* | |
H16C | 0.2781 | 0.3894 | 1.1261 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.05237 (15) | 0.05020 (14) | 0.03012 (11) | −0.00306 (11) | −0.00293 (9) | −0.00516 (9) |
S1 | 0.0285 (2) | 0.0376 (3) | 0.0274 (2) | −0.0057 (2) | 0.00289 (18) | −0.00232 (19) |
F4 | 0.0685 (9) | 0.0376 (7) | 0.0489 (8) | −0.0167 (7) | 0.0057 (7) | −0.0092 (6) |
O3 | 0.0422 (9) | 0.0591 (10) | 0.0385 (8) | 0.0009 (7) | 0.0153 (7) | −0.0034 (7) |
O2 | 0.0376 (9) | 0.0477 (10) | 0.0733 (12) | 0.0126 (7) | 0.0044 (8) | 0.0180 (9) |
O1 | 0.0390 (9) | 0.0724 (12) | 0.0530 (10) | 0.0034 (8) | 0.0143 (8) | −0.0143 (9) |
N8 | 0.0301 (9) | 0.0276 (8) | 0.0544 (11) | −0.0014 (7) | 0.0066 (8) | −0.0011 (8) |
C6 | 0.0260 (9) | 0.0271 (9) | 0.0274 (9) | 0.0028 (7) | 0.0091 (7) | 0.0009 (7) |
C1 | 0.0301 (9) | 0.0346 (10) | 0.0264 (9) | 0.0027 (8) | 0.0068 (7) | −0.0023 (8) |
C8 | 0.0278 (9) | 0.0244 (9) | 0.0371 (10) | −0.0008 (7) | 0.0044 (8) | 0.0026 (8) |
C7 | 0.0290 (9) | 0.0277 (9) | 0.0287 (9) | 0.0002 (8) | 0.0059 (7) | −0.0012 (7) |
C11 | 0.0319 (10) | 0.0275 (9) | 0.0250 (9) | −0.0046 (7) | 0.0046 (7) | 0.0031 (7) |
C12 | 0.0302 (9) | 0.0353 (10) | 0.0291 (9) | −0.0052 (8) | 0.0032 (8) | 0.0031 (8) |
C10 | 0.0339 (10) | 0.0275 (9) | 0.0281 (9) | −0.0027 (8) | 0.0019 (8) | 0.0059 (7) |
C5 | 0.0326 (10) | 0.0312 (10) | 0.0257 (9) | 0.0012 (8) | 0.0070 (7) | −0.0004 (8) |
C2 | 0.0422 (11) | 0.0393 (11) | 0.0309 (10) | 0.0086 (9) | 0.0099 (9) | 0.0083 (9) |
C9 | 0.0318 (10) | 0.0301 (10) | 0.0341 (10) | −0.0011 (8) | 0.0000 (8) | 0.0073 (8) |
C4 | 0.0378 (11) | 0.0312 (10) | 0.0362 (10) | −0.0032 (8) | 0.0114 (8) | −0.0058 (8) |
C14 | 0.0479 (12) | 0.0390 (11) | 0.0272 (10) | −0.0054 (10) | 0.0081 (9) | −0.0003 (8) |
C15 | 0.0381 (11) | 0.0369 (11) | 0.0273 (9) | −0.0032 (9) | −0.0010 (8) | 0.0042 (8) |
C13 | 0.0370 (11) | 0.0341 (10) | 0.0341 (10) | −0.0042 (9) | 0.0115 (8) | 0.0020 (8) |
C3 | 0.0469 (12) | 0.0295 (10) | 0.0421 (11) | 0.0029 (9) | 0.0169 (10) | 0.0051 (9) |
C16 | 0.0579 (15) | 0.0655 (16) | 0.0437 (13) | −0.0029 (13) | 0.0256 (12) | −0.0042 (12) |
Br1—C1 | 1.8961 (19) | C12—H12 | 0.9300 |
S1—C7 | 1.8307 (19) | C12—C13 | 1.392 (3) |
S1—C11 | 1.7574 (19) | C10—C9 | 1.440 (3) |
F4—C4 | 1.357 (2) | C10—C15 | 1.398 (3) |
O3—C13 | 1.355 (3) | C5—H5 | 0.9300 |
O3—C16 | 1.426 (3) | C5—C4 | 1.374 (3) |
O2—N8 | 1.221 (2) | C2—H2 | 0.9300 |
O1—N8 | 1.232 (2) | C2—C3 | 1.380 (3) |
N8—C8 | 1.460 (3) | C9—H9 | 0.9300 |
C6—C1 | 1.394 (3) | C4—C3 | 1.370 (3) |
C6—C7 | 1.516 (3) | C14—H14 | 0.9300 |
C6—C5 | 1.395 (3) | C14—C15 | 1.376 (3) |
C1—C2 | 1.379 (3) | C14—C13 | 1.393 (3) |
C8—C7 | 1.497 (3) | C15—H15 | 0.9300 |
C8—C9 | 1.332 (3) | C3—H3 | 0.9300 |
C7—H7 | 0.9800 | C16—H16A | 0.9600 |
C11—C12 | 1.377 (3) | C16—H16B | 0.9600 |
C11—C10 | 1.410 (3) | C16—H16C | 0.9600 |
C11—S1—C7 | 100.47 (9) | C4—C5—C6 | 119.55 (18) |
C13—O3—C16 | 117.99 (18) | C4—C5—H5 | 120.2 |
O2—N8—O1 | 123.58 (19) | C1—C2—H2 | 119.8 |
O2—N8—C8 | 119.36 (19) | C1—C2—C3 | 120.50 (19) |
O1—N8—C8 | 117.04 (17) | C3—C2—H2 | 119.8 |
C1—C6—C7 | 121.27 (17) | C8—C9—C10 | 123.18 (18) |
C1—C6—C5 | 117.40 (17) | C8—C9—H9 | 118.4 |
C5—C6—C7 | 121.32 (16) | C10—C9—H9 | 118.4 |
C6—C1—Br1 | 120.14 (15) | F4—C4—C5 | 117.72 (18) |
C2—C1—Br1 | 118.09 (15) | F4—C4—C3 | 119.08 (19) |
C2—C1—C6 | 121.77 (18) | C3—C4—C5 | 123.20 (19) |
N8—C8—C7 | 115.63 (17) | C15—C14—H14 | 120.5 |
C9—C8—N8 | 118.44 (18) | C15—C14—C13 | 118.98 (19) |
C9—C8—C7 | 125.74 (18) | C13—C14—H14 | 120.5 |
S1—C7—H7 | 107.0 | C10—C15—H15 | 118.8 |
C6—C7—S1 | 111.58 (13) | C14—C15—C10 | 122.39 (19) |
C6—C7—H7 | 107.0 | C14—C15—H15 | 118.8 |
C8—C7—S1 | 108.90 (13) | O3—C13—C12 | 115.12 (18) |
C8—C7—C6 | 114.88 (15) | O3—C13—C14 | 124.95 (19) |
C8—C7—H7 | 107.0 | C12—C13—C14 | 119.93 (19) |
C12—C11—S1 | 118.22 (14) | C2—C3—H3 | 121.2 |
C12—C11—C10 | 120.41 (18) | C4—C3—C2 | 117.55 (19) |
C10—C11—S1 | 121.01 (15) | C4—C3—H3 | 121.2 |
C11—C12—H12 | 119.7 | O3—C16—H16A | 109.5 |
C11—C12—C13 | 120.61 (18) | O3—C16—H16B | 109.5 |
C13—C12—H12 | 119.7 | O3—C16—H16C | 109.5 |
C11—C10—C9 | 121.27 (18) | H16A—C16—H16B | 109.5 |
C15—C10—C11 | 117.59 (19) | H16A—C16—H16C | 109.5 |
C15—C10—C9 | 121.07 (18) | H16B—C16—H16C | 109.5 |
C6—C5—H5 | 120.2 |
Cg3 is the centroid of the C10–C15 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O1i | 0.93 | 2.60 | 3.418 (3) | 148 |
C15—H15···F4ii | 0.93 | 2.54 | 3.268 (2) | 136 |
C16—C16B···Cg3iii | 0.96 | 2.86 | 3.668 (3) | 143 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+1, −z+2. |
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