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(2
R,4
S)-2-(3-Methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-
b]azepine, C
19H
17NOS, (I), crystallizes with a single enantiomer in each crystal, whereas its geometrical isomer (2
RS,4
SR)-2-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-naphtho[1,2-
b]azepine, (II), and (2
RS,4
SR)-2-(5-bromothiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-
b]azepine, C
18H
14BrNOS, (III), both crystallize as racemic mixtures. A combination of one C-H
O hydrogen bond and two C-H
(arene) hydrogen bonds links the molecules of (I) into a three-dimensional framework; the molecules of (II) are linked into a
C(4)
C(4)[
R22(7)] chain of rings by a combination of C-H
N and C-H
O hydrogen bonds; and in (III), where
Z' = 2, a combination of four C-H
(arene) hydrogen bonds and two C-H
(thienyl) hydrogen bonds links the molecules into complex sheets. Comparisons are made with the assembly patterns in some aryl-substituted 1,4-epoxynaphtho[1,2-
b]azepines.
Supporting information
CCDC references: 934587; 934588; 934589
For the preparation of compounds (I)–(III), sodium tungstate dihydrate and
Na2WO4.2H2O (5–10 mol%), followed by 30% aqueous hydrogen peroxide
solution (30 mmol), were added to a stirred and cooled (273 K) solution of the
appropriately substituted 2-allyl-N-(thienylmethyl)naphthalen-1-amine
(10 mmol) in acetone–water (20 ml, 10:1 v/v). The resulting
mixtures were stirred at 273 K for 2 h, and then at ambient temperature for
periods ranging from 60 to 72 h. Each mixture was filtered and the solvent
removed under reduced pressure. Toluene (30 ml) was added to the organic
residue and the resulting solution was heated at 363–373 K for 12–13 h.
After cooling each solution to ambient temperature, the solvent was removed
under reduced pressure and the crude product was purified by chromatography on
silica using heptane–ethyl acetate (compositions ranged from 30:1 to 10:1
v/v) as eluent. Crystallization from heptane, at ambient
temperature and exposed to air, gave pale-yellow crystals of compounds
(I)–(III) suitable for single-crystal X-ray diffraction. Data for (I): yield
45%, m.p. 422–423 K; MS (70 eV) m/z (%): 307 (M+, 14),
277 (3), 264 (14), 180 (9), 154 (3), 142 (100), 115 (31); HR–MS (EI), found
307.1029, C19H17NOS requires 307.1031. Data for (II): yield 50%, m.p.
404–405 K; MS (70 eV) m/z (%): 307 (M+, 18), 277 (4),
264 (30), 180 (8), 154 (4), 142 (100), 115 (25); HR–MS (EI), found 307.1029;
C19H17NOS requires 307.1031. Data for (III): yield 49%, m.p. 407–408 K;
MS (70 eV) m/z (%): 371 (M+, 79Br, 8), 341 (4), 328
(7), 180 (5), 154 (2), 142 (100), 115 (27); HR–MS (EI), found 371.2789;
C18H14BrNOS requires 371.2791.
All H atoms were located in difference maps and then treated as riding atoms in
geometrically idealized positions, with C—H = 0.95 (aryl and thienyl), 0.98
(CH3), 0.99 (CH2) or 1.00 Å (aliphatic) and with Uiso(H)=
kUeq(C), where k = 1.5 for methyl groups, which were permitted
to rotate but not to tilt, and 1.2 for all other H atoms. For (I), the
(2R,4S) configuration was confirmed for the crystal selected for
data collection by the value of the Flack x parameter (Flack, 1983) and
the Hooft y parameter (Hooft et al., 2008), i.e. x =
0.03 (9) and y = -0.05 (6) for 1333 Bijvoet pairs (92.5% coverage).
Because of the rather weak diffraction observed in (I), data having θ >
25.5° were omitted from the final refinements. Compounds (II) and (III) both
crystallize as racemic mixtures of (2R,4S) and
(2S,4R) forms in the space groups P21/c and
Pna21, respectively. Compound (III) was handled as an inversion twin,
giving twin fractions for the crystal selected for data collection of 0.658 (9)
and 0.342 (9). Accordingly, the (2R,4S) configuration was
selected for the reference molecule of (II) and for both of the independent
molecules in (III).
For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) (2
R,4
S)-2-(3-Methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-
b]-azepine
top
Crystal data top
C19H17NOS | F(000) = 648 |
Mr = 307.41 | Dx = 1.379 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3274 reflections |
a = 7.0387 (3) Å | θ = 2.9–27.5° |
b = 11.5605 (10) Å | µ = 0.22 mm−1 |
c = 18.1951 (17) Å | T = 120 K |
V = 1480.6 (2) Å3 | Block, pale yellow |
Z = 4 | 0.34 × 0.24 × 0.14 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2698 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1838 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.129 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.9° |
ϕ & ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.929, Tmax = 0.970 | l = −22→20 |
13622 measured reflections | |
Refinement top
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0405P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
2698 reflections | Δρmax = 0.43 e Å−3 |
200 parameters | Δρmin = −0.62 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1333 Bijvoet pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (9) |
Crystal data top
C19H17NOS | V = 1480.6 (2) Å3 |
Mr = 307.41 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.0387 (3) Å | µ = 0.22 mm−1 |
b = 11.5605 (10) Å | T = 120 K |
c = 18.1951 (17) Å | 0.34 × 0.24 × 0.14 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2698 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1838 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.970 | Rint = 0.129 |
13622 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.083 | Δρmax = 0.43 e Å−3 |
S = 0.99 | Δρmin = −0.62 e Å−3 |
2698 reflections | Absolute structure: Flack (1983), 1333 Bijvoet pairs |
200 parameters | Absolute structure parameter: 0.03 (9) |
0 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.4464 (3) | 0.5357 (2) | 0.42589 (11) | 0.0185 (5) | |
C2 | 0.3887 (3) | 0.4542 (3) | 0.48391 (13) | 0.0201 (6) | |
H2 | 0.3494 | 0.3796 | 0.4605 | 0.024* | |
C3 | 0.2132 (4) | 0.5115 (3) | 0.51853 (13) | 0.0217 (7) | |
H3A | 0.0953 | 0.4709 | 0.5038 | 0.026* | |
H3B | 0.2222 | 0.5117 | 0.5728 | 0.026* | |
C4 | 0.2167 (4) | 0.6340 (3) | 0.48831 (13) | 0.0215 (7) | |
H4 | 0.1913 | 0.6918 | 0.5280 | 0.026* | |
C5 | 0.0844 (4) | 0.6519 (3) | 0.42413 (14) | 0.0233 (7) | |
H5A | −0.0470 | 0.6313 | 0.4385 | 0.028* | |
H5B | 0.0858 | 0.7342 | 0.4091 | 0.028* | |
C5A | 0.1471 (3) | 0.5773 (3) | 0.36132 (14) | 0.0189 (7) | |
C6 | 0.0290 (4) | 0.5591 (3) | 0.30023 (14) | 0.0243 (7) | |
H6 | −0.0882 | 0.5996 | 0.2969 | 0.029* | |
C7 | 0.0790 (4) | 0.4850 (3) | 0.24605 (14) | 0.0265 (8) | |
H7 | −0.0046 | 0.4732 | 0.2058 | 0.032* | |
C7A | 0.2524 (4) | 0.4254 (3) | 0.24846 (13) | 0.0207 (7) | |
C8 | 0.3043 (4) | 0.3437 (3) | 0.19527 (14) | 0.0262 (7) | |
H8 | 0.2190 | 0.3271 | 0.1562 | 0.031* | |
C9 | 0.4721 (4) | 0.2883 (3) | 0.19826 (15) | 0.0328 (8) | |
H9 | 0.5036 | 0.2328 | 0.1617 | 0.039* | |
C10 | 0.6009 (4) | 0.3123 (3) | 0.25514 (15) | 0.0311 (8) | |
H10 | 0.7202 | 0.2740 | 0.2564 | 0.037* | |
C11 | 0.5559 (4) | 0.3898 (3) | 0.30819 (14) | 0.0229 (7) | |
H11 | 0.6446 | 0.4058 | 0.3462 | 0.028* | |
C11A | 0.3794 (4) | 0.4468 (3) | 0.30762 (13) | 0.0184 (7) | |
C11B | 0.3194 (3) | 0.5229 (3) | 0.36357 (13) | 0.0174 (6) | |
O14 | 0.4097 (2) | 0.64557 (18) | 0.46023 (9) | 0.0224 (5) | |
S21 | 0.71287 (9) | 0.53184 (8) | 0.56069 (4) | 0.0270 (2) | |
C22 | 0.5440 (3) | 0.4302 (3) | 0.53838 (13) | 0.0192 (7) | |
C23 | 0.5621 (4) | 0.3332 (3) | 0.57931 (14) | 0.0219 (7) | |
C24 | 0.7171 (4) | 0.3414 (3) | 0.62838 (14) | 0.0258 (7) | |
H24 | 0.7515 | 0.2810 | 0.6612 | 0.031* | |
C25 | 0.8113 (4) | 0.4420 (3) | 0.62447 (14) | 0.0280 (8) | |
H25 | 0.9191 | 0.4608 | 0.6535 | 0.034* | |
C26 | 0.4321 (4) | 0.2351 (3) | 0.57507 (15) | 0.0311 (8) | |
H26A | 0.4298 | 0.2053 | 0.5247 | 0.047* | |
H26B | 0.3041 | 0.2602 | 0.5891 | 0.047* | |
H26C | 0.4749 | 0.1741 | 0.6086 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0221 (11) | 0.0163 (14) | 0.0171 (11) | 0.0009 (11) | 0.0003 (9) | −0.0011 (11) |
C2 | 0.0212 (14) | 0.0213 (18) | 0.0179 (13) | −0.0013 (13) | 0.0021 (11) | 0.0033 (13) |
C3 | 0.0210 (14) | 0.026 (2) | 0.0180 (13) | 0.0032 (14) | 0.0020 (11) | 0.0011 (13) |
C4 | 0.0281 (16) | 0.0203 (18) | 0.0161 (13) | 0.0040 (14) | 0.0041 (12) | −0.0027 (13) |
C5 | 0.0261 (16) | 0.0180 (17) | 0.0258 (15) | 0.0053 (13) | 0.0008 (13) | 0.0010 (13) |
C5A | 0.0212 (16) | 0.0184 (18) | 0.0171 (14) | 0.0001 (12) | 0.0009 (10) | 0.0034 (13) |
C6 | 0.0242 (15) | 0.023 (2) | 0.0260 (15) | 0.0042 (13) | −0.0037 (12) | 0.0022 (15) |
C7 | 0.0276 (17) | 0.031 (2) | 0.0210 (14) | −0.0020 (15) | −0.0085 (12) | 0.0028 (15) |
C7A | 0.0306 (17) | 0.0173 (16) | 0.0142 (13) | −0.0032 (13) | 0.0011 (11) | 0.0026 (13) |
C8 | 0.0337 (18) | 0.027 (2) | 0.0175 (14) | −0.0015 (17) | −0.0008 (13) | −0.0016 (14) |
C9 | 0.049 (2) | 0.029 (2) | 0.0205 (16) | 0.0055 (16) | 0.0098 (15) | −0.0022 (16) |
C10 | 0.0288 (16) | 0.037 (2) | 0.0278 (16) | 0.0079 (16) | 0.0071 (14) | −0.0004 (16) |
C11 | 0.0245 (16) | 0.025 (2) | 0.0196 (14) | 0.0021 (14) | 0.0018 (12) | 0.0024 (14) |
C11A | 0.0216 (14) | 0.0171 (19) | 0.0165 (13) | −0.0023 (13) | 0.0024 (11) | 0.0063 (12) |
C11B | 0.0223 (15) | 0.0173 (17) | 0.0128 (12) | −0.0025 (14) | 0.0007 (10) | 0.0006 (13) |
O14 | 0.0257 (11) | 0.0198 (12) | 0.0218 (10) | −0.0006 (9) | −0.0008 (8) | −0.0031 (9) |
S21 | 0.0241 (4) | 0.0281 (5) | 0.0288 (4) | −0.0028 (4) | −0.0017 (3) | 0.0049 (4) |
C22 | 0.0173 (14) | 0.0222 (19) | 0.0181 (14) | 0.0039 (12) | 0.0066 (11) | −0.0001 (14) |
C23 | 0.0263 (16) | 0.0207 (19) | 0.0187 (14) | 0.0017 (13) | 0.0028 (12) | 0.0015 (14) |
C24 | 0.0290 (16) | 0.031 (2) | 0.0174 (14) | 0.0090 (16) | 0.0010 (13) | 0.0039 (14) |
C25 | 0.0229 (15) | 0.041 (3) | 0.0206 (15) | 0.0061 (16) | −0.0013 (12) | 0.0026 (15) |
C26 | 0.0336 (18) | 0.033 (2) | 0.0267 (16) | 0.0019 (15) | −0.0042 (14) | 0.0012 (16) |
Geometric parameters (Å, º) top
N1—O14 | 1.439 (3) | C7A—C11A | 1.421 (3) |
N1—C11B | 1.451 (3) | C8—C9 | 1.345 (4) |
N1—C2 | 1.472 (3) | C8—H8 | 0.9500 |
C2—C22 | 1.501 (3) | C9—C10 | 1.403 (4) |
C2—C3 | 1.537 (4) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C10—C11 | 1.354 (4) |
C3—C4 | 1.520 (4) | C10—H10 | 0.9500 |
C3—H3A | 0.9900 | C11—C11A | 1.407 (4) |
C3—H3B | 0.9900 | C11—H11 | 0.9500 |
C4—O14 | 1.458 (3) | C11A—C11B | 1.410 (4) |
C4—C5 | 1.508 (4) | S21—C25 | 1.704 (3) |
C4—H4 | 1.0000 | S21—C22 | 1.720 (3) |
C5—C5A | 1.498 (4) | C22—C23 | 1.352 (4) |
C5—H5A | 0.9900 | C23—C24 | 1.413 (4) |
C5—H5B | 0.9900 | C23—C26 | 1.459 (4) |
C5A—C11B | 1.367 (3) | C24—C25 | 1.341 (5) |
C5A—C6 | 1.404 (3) | C24—H24 | 0.9500 |
C6—C7 | 1.353 (4) | C25—H25 | 0.9500 |
C6—H6 | 0.9500 | C26—H26A | 0.9800 |
C7—C7A | 1.403 (4) | C26—H26B | 0.9800 |
C7—H7 | 0.9500 | C26—H26C | 0.9800 |
C7A—C8 | 1.401 (4) | | |
| | | |
O14—N1—C11B | 108.61 (19) | C9—C8—C7A | 121.5 (3) |
O14—N1—C2 | 101.80 (18) | C9—C8—H8 | 119.3 |
C11B—N1—C2 | 109.0 (2) | C7A—C8—H8 | 119.3 |
N1—C2—C22 | 113.0 (2) | C8—C9—C10 | 120.2 (3) |
N1—C2—C3 | 103.8 (2) | C8—C9—H9 | 119.9 |
C22—C2—C3 | 113.2 (2) | C10—C9—H9 | 119.9 |
N1—C2—H2 | 108.8 | C11—C10—C9 | 120.4 (3) |
C22—C2—H2 | 108.8 | C11—C10—H10 | 119.8 |
C3—C2—H2 | 108.8 | C9—C10—H10 | 119.8 |
C4—C3—C2 | 103.9 (2) | C10—C11—C11A | 120.7 (3) |
C4—C3—H3A | 111.0 | C10—C11—H11 | 119.6 |
C2—C3—H3A | 111.0 | C11A—C11—H11 | 119.6 |
C4—C3—H3B | 111.0 | C11—C11A—C11B | 123.5 (2) |
C2—C3—H3B | 111.0 | C11—C11A—C7A | 118.7 (3) |
H3A—C3—H3B | 109.0 | C11B—C11A—C7A | 117.9 (2) |
O14—C4—C5 | 106.96 (19) | C5A—C11B—C11A | 122.1 (2) |
O14—C4—C3 | 103.2 (2) | C5A—C11B—N1 | 121.5 (2) |
C5—C4—C3 | 113.4 (2) | C11A—C11B—N1 | 116.3 (2) |
O14—C4—H4 | 111.0 | N1—O14—C4 | 103.80 (19) |
C5—C4—H4 | 111.0 | C25—S21—C22 | 91.45 (15) |
C3—C4—H4 | 111.0 | C23—C22—C2 | 125.8 (3) |
C5A—C5—C4 | 109.3 (2) | C23—C22—S21 | 111.82 (19) |
C5A—C5—H5A | 109.8 | C2—C22—S21 | 122.2 (2) |
C4—C5—H5A | 109.8 | C22—C23—C24 | 111.4 (3) |
C5A—C5—H5B | 109.8 | C22—C23—C26 | 123.8 (2) |
C4—C5—H5B | 109.8 | C24—C23—C26 | 124.7 (3) |
H5A—C5—H5B | 108.3 | C25—C24—C23 | 114.0 (3) |
C11B—C5A—C6 | 118.7 (3) | C25—C24—H24 | 123.0 |
C11B—C5A—C5 | 120.2 (2) | C23—C24—H24 | 123.0 |
C6—C5A—C5 | 121.0 (2) | C24—C25—S21 | 111.3 (2) |
C7—C6—C5A | 121.2 (3) | C24—C25—H25 | 124.3 |
C7—C6—H6 | 119.4 | S21—C25—H25 | 124.3 |
C5A—C6—H6 | 119.4 | C23—C26—H26A | 109.5 |
C6—C7—C7A | 121.0 (2) | C23—C26—H26B | 109.5 |
C6—C7—H7 | 119.5 | H26A—C26—H26B | 109.5 |
C7A—C7—H7 | 119.5 | C23—C26—H26C | 109.5 |
C8—C7A—C7 | 122.5 (2) | H26A—C26—H26C | 109.5 |
C8—C7A—C11A | 118.5 (2) | H26B—C26—H26C | 109.5 |
C7—C7A—C11A | 119.1 (3) | | |
| | | |
O14—N1—C2—C22 | −85.4 (2) | C5—C5A—C11B—C11A | 176.3 (3) |
C11B—N1—C2—C22 | 160.0 (2) | C6—C5A—C11B—N1 | −178.5 (3) |
O14—N1—C2—C3 | 37.7 (2) | C5—C5A—C11B—N1 | −0.3 (4) |
C11B—N1—C2—C3 | −76.9 (2) | C11—C11A—C11B—C5A | 179.8 (3) |
N1—C2—C3—C4 | −13.0 (3) | C7A—C11A—C11B—C5A | −1.5 (4) |
C22—C2—C3—C4 | 110.0 (3) | C11—C11A—C11B—N1 | −3.4 (4) |
C2—C3—C4—O14 | −16.1 (2) | C7A—C11A—C11B—N1 | 175.4 (2) |
C2—C3—C4—C5 | 99.2 (2) | O14—N1—C11B—C5A | −27.1 (3) |
O14—C4—C5—C5A | 49.5 (3) | C2—N1—C11B—C5A | 83.0 (3) |
C3—C4—C5—C5A | −63.5 (3) | O14—N1—C11B—C11A | 156.1 (2) |
C4—C5—C5A—C11B | −11.0 (4) | C2—N1—C11B—C11A | −93.8 (3) |
C4—C5—C5A—C6 | 167.0 (3) | C11B—N1—O14—C4 | 65.2 (2) |
C11B—C5A—C6—C7 | 3.2 (4) | C2—N1—O14—C4 | −49.65 (19) |
C5—C5A—C6—C7 | −174.9 (3) | C5—C4—O14—N1 | −79.2 (2) |
C5A—C6—C7—C7A | −1.2 (5) | C3—C4—O14—N1 | 40.7 (2) |
C6—C7—C7A—C8 | 176.7 (3) | N1—C2—C22—C23 | −154.1 (3) |
C6—C7—C7A—C11A | −2.2 (4) | C3—C2—C22—C23 | 88.2 (3) |
C7—C7A—C8—C9 | 179.4 (3) | N1—C2—C22—S21 | 31.1 (3) |
C11A—C7A—C8—C9 | −1.8 (4) | C3—C2—C22—S21 | −86.6 (3) |
C7A—C8—C9—C10 | −0.5 (5) | C25—S21—C22—C23 | 1.1 (2) |
C8—C9—C10—C11 | 1.2 (5) | C25—S21—C22—C2 | 176.5 (2) |
C9—C10—C11—C11A | 0.5 (5) | C2—C22—C23—C24 | −176.3 (2) |
C10—C11—C11A—C11B | 176.0 (3) | S21—C22—C23—C24 | −1.0 (3) |
C10—C11—C11A—C7A | −2.8 (4) | C2—C22—C23—C26 | 1.3 (4) |
C8—C7A—C11A—C11 | 3.4 (4) | S21—C22—C23—C26 | 176.5 (2) |
C7—C7A—C11A—C11 | −177.7 (3) | C22—C23—C24—C25 | 0.4 (3) |
C8—C7A—C11A—C11B | −175.5 (3) | C26—C23—C24—C25 | −177.1 (3) |
C7—C7A—C11A—C11B | 3.5 (4) | C23—C24—C25—S21 | 0.4 (3) |
C6—C5A—C11B—C11A | −1.8 (4) | C22—S21—C25—C24 | −0.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O14i | 0.95 | 2.51 | 3.425 (3) | 161 |
C7—H7···Cg1ii | 0.95 | 2.78 | 3.582 (3) | 143 |
C24—H24···Cg2iii | 0.95 | 2.64 | 3.572 (3) | 167 |
C25—H25···Cg2iv | 0.95 | 2.88 | 3.690 (3) | 143 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+3/2, −y+1, z+1/2. |
(II) (2
RS,4
SR)-2-(5-Methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-naphtho[1,2-
b]azepine
top
Crystal data top
C19H17NOS | F(000) = 648 |
Mr = 307.41 | Dx = 1.370 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3412 reflections |
a = 16.165 (2) Å | θ = 3.3–27.5° |
b = 5.2505 (3) Å | µ = 0.22 mm−1 |
c = 20.0410 (19) Å | T = 120 K |
β = 118.813 (9)° | Block, pale yellow |
V = 1490.4 (3) Å3 | 0.41 × 0.23 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3412 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2058 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ & ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→6 |
Tmin = 0.916, Tmax = 0.974 | l = −26→26 |
20766 measured reflections | |
Refinement top
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0603P)2 + 1.3536P] where P = (Fo2 + 2Fc2)/3 |
3412 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C19H17NOS | V = 1490.4 (3) Å3 |
Mr = 307.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.165 (2) Å | µ = 0.22 mm−1 |
b = 5.2505 (3) Å | T = 120 K |
c = 20.0410 (19) Å | 0.41 × 0.23 × 0.12 mm |
β = 118.813 (9)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3412 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2058 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.974 | Rint = 0.082 |
20766 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.35 e Å−3 |
3412 reflections | Δρmin = −0.31 e Å−3 |
200 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.20849 (15) | 0.4955 (4) | 0.58378 (12) | 0.0225 (5) | |
C2 | 0.20137 (19) | 0.3317 (5) | 0.64226 (15) | 0.0236 (6) | |
H2 | 0.2645 | 0.2562 | 0.6771 | 0.028* | |
C3 | 0.1322 (2) | 0.1187 (5) | 0.59562 (15) | 0.0260 (6) | |
H3A | 0.1656 | −0.0450 | 0.6022 | 0.031* | |
H3B | 0.0826 | 0.0962 | 0.6107 | 0.031* | |
C4 | 0.08977 (19) | 0.2145 (5) | 0.51330 (16) | 0.0256 (6) | |
H4 | 0.0198 | 0.1884 | 0.4854 | 0.031* | |
C5 | 0.13543 (19) | 0.0953 (5) | 0.47049 (16) | 0.0254 (6) | |
H5A | 0.1002 | 0.1441 | 0.4161 | 0.030* | |
H5B | 0.1339 | −0.0926 | 0.4739 | 0.030* | |
C5A | 0.23657 (18) | 0.1854 (5) | 0.50444 (15) | 0.0222 (6) | |
C6 | 0.2985 (2) | 0.0794 (6) | 0.48050 (17) | 0.0284 (7) | |
H6 | 0.2764 | −0.0524 | 0.4434 | 0.034* | |
C7 | 0.3895 (2) | 0.1626 (6) | 0.50958 (16) | 0.0295 (7) | |
H7 | 0.4295 | 0.0885 | 0.4925 | 0.035* | |
C7A | 0.42474 (19) | 0.3595 (6) | 0.56531 (16) | 0.0271 (7) | |
C8 | 0.5183 (2) | 0.4530 (6) | 0.59578 (18) | 0.0340 (8) | |
H8 | 0.5598 | 0.3804 | 0.5798 | 0.041* | |
C9 | 0.5494 (2) | 0.6460 (6) | 0.64768 (18) | 0.0362 (8) | |
H9 | 0.6120 | 0.7077 | 0.6672 | 0.043* | |
C10 | 0.4893 (2) | 0.7550 (6) | 0.67268 (17) | 0.0335 (7) | |
H10 | 0.5119 | 0.8883 | 0.7092 | 0.040* | |
C11 | 0.39863 (19) | 0.6699 (5) | 0.64465 (15) | 0.0256 (6) | |
H11 | 0.3586 | 0.7453 | 0.6616 | 0.031* | |
C11A | 0.36397 (19) | 0.4697 (5) | 0.59045 (15) | 0.0243 (6) | |
C11B | 0.26945 (18) | 0.3749 (5) | 0.55810 (15) | 0.0221 (6) | |
O14 | 0.11286 (12) | 0.4854 (4) | 0.52181 (11) | 0.0246 (5) | |
S21 | 0.24866 (5) | 0.68266 (15) | 0.75998 (4) | 0.0280 (2) | |
C22 | 0.16870 (19) | 0.4907 (5) | 0.68786 (15) | 0.0241 (6) | |
C23 | 0.0807 (2) | 0.5227 (6) | 0.68014 (16) | 0.0276 (7) | |
H23 | 0.0264 | 0.4355 | 0.6432 | 0.033* | |
C24 | 0.0786 (2) | 0.6992 (6) | 0.73283 (16) | 0.0290 (7) | |
H24 | 0.0227 | 0.7392 | 0.7351 | 0.035* | |
C25 | 0.1639 (2) | 0.8060 (6) | 0.77980 (16) | 0.0267 (6) | |
C26 | 0.1882 (2) | 1.0026 (6) | 0.84045 (17) | 0.0340 (7) | |
H26A | 0.1785 | 1.1729 | 0.8179 | 0.051* | |
H26B | 0.2544 | 0.9830 | 0.8794 | 0.051* | |
H26C | 0.1475 | 0.9807 | 0.8638 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0212 (12) | 0.0232 (13) | 0.0226 (12) | 0.0005 (10) | 0.0102 (10) | 0.0019 (10) |
C2 | 0.0259 (14) | 0.0212 (15) | 0.0249 (14) | 0.0012 (12) | 0.0132 (12) | 0.0004 (12) |
C3 | 0.0331 (16) | 0.0214 (15) | 0.0272 (15) | −0.0012 (12) | 0.0175 (14) | 0.0003 (12) |
C4 | 0.0239 (14) | 0.0245 (16) | 0.0278 (15) | −0.0045 (12) | 0.0120 (12) | −0.0012 (13) |
C5 | 0.0319 (15) | 0.0219 (15) | 0.0217 (14) | −0.0024 (12) | 0.0125 (13) | −0.0018 (12) |
C5A | 0.0266 (14) | 0.0194 (14) | 0.0214 (14) | 0.0032 (12) | 0.0124 (12) | 0.0046 (12) |
C6 | 0.0328 (16) | 0.0249 (16) | 0.0271 (15) | 0.0038 (13) | 0.0142 (14) | 0.0018 (13) |
C7 | 0.0306 (15) | 0.0336 (18) | 0.0280 (16) | 0.0083 (13) | 0.0171 (13) | 0.0030 (14) |
C7A | 0.0250 (14) | 0.0305 (17) | 0.0252 (15) | 0.0026 (12) | 0.0117 (12) | 0.0052 (13) |
C8 | 0.0248 (15) | 0.042 (2) | 0.0354 (18) | 0.0042 (14) | 0.0151 (14) | 0.0052 (15) |
C9 | 0.0242 (15) | 0.045 (2) | 0.0348 (17) | −0.0004 (14) | 0.0107 (14) | 0.0060 (16) |
C10 | 0.0322 (16) | 0.0377 (19) | 0.0263 (16) | −0.0064 (14) | 0.0107 (14) | −0.0013 (14) |
C11 | 0.0294 (15) | 0.0246 (15) | 0.0240 (14) | −0.0016 (13) | 0.0138 (12) | −0.0001 (13) |
C11A | 0.0272 (15) | 0.0226 (15) | 0.0221 (14) | 0.0022 (12) | 0.0110 (12) | 0.0033 (12) |
C11B | 0.0238 (14) | 0.0228 (15) | 0.0208 (14) | 0.0051 (11) | 0.0117 (12) | 0.0044 (12) |
O14 | 0.0218 (9) | 0.0217 (11) | 0.0272 (11) | 0.0001 (8) | 0.0092 (8) | 0.0012 (9) |
S21 | 0.0265 (4) | 0.0291 (4) | 0.0268 (4) | −0.0012 (3) | 0.0114 (3) | −0.0042 (3) |
C22 | 0.0286 (15) | 0.0211 (14) | 0.0238 (15) | 0.0002 (12) | 0.0137 (13) | 0.0018 (12) |
C23 | 0.0258 (15) | 0.0288 (17) | 0.0259 (15) | −0.0010 (13) | 0.0106 (12) | −0.0024 (13) |
C24 | 0.0308 (15) | 0.0308 (17) | 0.0326 (16) | 0.0031 (13) | 0.0209 (14) | −0.0009 (14) |
C25 | 0.0335 (16) | 0.0266 (16) | 0.0235 (15) | 0.0004 (13) | 0.0164 (13) | −0.0001 (13) |
C26 | 0.0433 (18) | 0.0303 (17) | 0.0302 (16) | 0.0040 (14) | 0.0192 (15) | −0.0044 (14) |
Geometric parameters (Å, º) top
N1—O14 | 1.444 (3) | C7A—C11A | 1.425 (4) |
N1—C11B | 1.458 (3) | C8—C9 | 1.363 (4) |
N1—C2 | 1.502 (3) | C8—H8 | 0.9500 |
C2—C22 | 1.509 (4) | C9—C10 | 1.411 (4) |
C2—C3 | 1.539 (4) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C10—C11 | 1.367 (4) |
C3—C4 | 1.534 (4) | C10—H10 | 0.9500 |
C3—H3A | 0.9900 | C11—C11A | 1.418 (4) |
C3—H3B | 0.9900 | C11—H11 | 0.9500 |
C4—O14 | 1.459 (3) | C11A—C11B | 1.431 (4) |
C4—C5 | 1.511 (4) | S21—C22 | 1.725 (3) |
C4—H4 | 1.0000 | S21—C25 | 1.726 (3) |
C5—C5A | 1.512 (4) | C22—C23 | 1.364 (4) |
C5—H5A | 0.9900 | C23—C24 | 1.418 (4) |
C5—H5B | 0.9900 | C23—H23 | 0.9500 |
C5A—C11B | 1.370 (4) | C24—C25 | 1.360 (4) |
C5A—C6 | 1.417 (4) | C24—H24 | 0.9500 |
C6—C7 | 1.366 (4) | C25—C26 | 1.496 (4) |
C6—H6 | 0.9500 | C26—H26A | 0.9800 |
C7—C7A | 1.424 (4) | C26—H26B | 0.9800 |
C7—H7 | 0.9500 | C26—H26C | 0.9800 |
C7A—C8 | 1.418 (4) | | |
| | | |
O14—N1—C11B | 107.81 (19) | C9—C8—C7A | 120.7 (3) |
O14—N1—C2 | 101.36 (18) | C9—C8—H8 | 119.7 |
C11B—N1—C2 | 110.2 (2) | C7A—C8—H8 | 119.7 |
N1—C2—C22 | 109.6 (2) | C8—C9—C10 | 120.6 (3) |
N1—C2—C3 | 104.4 (2) | C8—C9—H9 | 119.7 |
C22—C2—C3 | 113.9 (2) | C10—C9—H9 | 119.7 |
N1—C2—H2 | 109.6 | C11—C10—C9 | 120.4 (3) |
C22—C2—H2 | 109.6 | C11—C10—H10 | 119.8 |
C3—C2—H2 | 109.6 | C9—C10—H10 | 119.8 |
C4—C3—C2 | 103.4 (2) | C10—C11—C11A | 120.4 (3) |
C4—C3—H3A | 111.1 | C10—C11—H11 | 119.8 |
C2—C3—H3A | 111.1 | C11A—C11—H11 | 119.8 |
C4—C3—H3B | 111.1 | C11—C11A—C7A | 119.1 (3) |
C2—C3—H3B | 111.1 | C11—C11A—C11B | 123.1 (3) |
H3A—C3—H3B | 109.0 | C7A—C11A—C11B | 117.8 (3) |
O14—C4—C5 | 107.6 (2) | C5A—C11B—C11A | 122.3 (2) |
O14—C4—C3 | 103.7 (2) | C5A—C11B—N1 | 121.3 (2) |
C5—C4—C3 | 112.8 (2) | C11A—C11B—N1 | 116.4 (2) |
O14—C4—H4 | 110.8 | N1—O14—C4 | 104.13 (18) |
C5—C4—H4 | 110.8 | C22—S21—C25 | 93.13 (13) |
C3—C4—H4 | 110.8 | C23—C22—C2 | 130.5 (3) |
C4—C5—C5A | 109.5 (2) | C23—C22—S21 | 110.0 (2) |
C4—C5—H5A | 109.8 | C2—C22—S21 | 119.42 (19) |
C5A—C5—H5A | 109.8 | C22—C23—C24 | 113.2 (3) |
C4—C5—H5B | 109.8 | C22—C23—H23 | 123.4 |
C5A—C5—H5B | 109.8 | C24—C23—H23 | 123.4 |
H5A—C5—H5B | 108.2 | C25—C24—C23 | 113.9 (3) |
C11B—C5A—C6 | 118.7 (3) | C25—C24—H24 | 123.1 |
C11B—C5A—C5 | 120.4 (2) | C23—C24—H24 | 123.1 |
C6—C5A—C5 | 120.8 (3) | C24—C25—C26 | 129.0 (3) |
C7—C6—C5A | 121.4 (3) | C24—C25—S21 | 109.8 (2) |
C7—C6—H6 | 119.3 | C26—C25—S21 | 121.3 (2) |
C5A—C6—H6 | 119.3 | C25—C26—H26A | 109.5 |
C6—C7—C7A | 120.6 (3) | C25—C26—H26B | 109.5 |
C6—C7—H7 | 119.7 | H26A—C26—H26B | 109.5 |
C7A—C7—H7 | 119.7 | C25—C26—H26C | 109.5 |
C8—C7A—C7 | 122.0 (3) | H26A—C26—H26C | 109.5 |
C8—C7A—C11A | 118.7 (3) | H26B—C26—H26C | 109.5 |
C7—C7A—C11A | 119.3 (3) | | |
| | | |
O14—N1—C2—C22 | −85.8 (2) | C5—C5A—C11B—C11A | −178.6 (2) |
C11B—N1—C2—C22 | 160.2 (2) | C6—C5A—C11B—N1 | 178.6 (2) |
O14—N1—C2—C3 | 36.6 (2) | C5—C5A—C11B—N1 | −0.2 (4) |
C11B—N1—C2—C3 | −77.4 (2) | C11—C11A—C11B—C5A | 178.4 (3) |
N1—C2—C3—C4 | −11.9 (3) | C7A—C11A—C11B—C5A | −0.3 (4) |
C22—C2—C3—C4 | 107.7 (3) | C11—C11A—C11B—N1 | 0.0 (4) |
C2—C3—C4—O14 | −16.8 (3) | C7A—C11A—C11B—N1 | −178.7 (2) |
C2—C3—C4—C5 | 99.3 (3) | O14—N1—C11B—C5A | −29.1 (3) |
O14—C4—C5—C5A | 46.5 (3) | C2—N1—C11B—C5A | 80.7 (3) |
C3—C4—C5—C5A | −67.3 (3) | O14—N1—C11B—C11A | 149.3 (2) |
C4—C5—C5A—C11B | −8.5 (4) | C2—N1—C11B—C11A | −100.9 (3) |
C4—C5—C5A—C6 | 172.7 (2) | C11B—N1—O14—C4 | 67.0 (2) |
C11B—C5A—C6—C7 | −0.2 (4) | C2—N1—O14—C4 | −48.8 (2) |
C5—C5A—C6—C7 | 178.7 (3) | C5—C4—O14—N1 | −78.5 (2) |
C5A—C6—C7—C7A | 0.1 (4) | C3—C4—O14—N1 | 41.2 (2) |
C6—C7—C7A—C8 | −179.0 (3) | N1—C2—C22—C23 | 97.2 (3) |
C6—C7—C7A—C11A | −0.1 (4) | C3—C2—C22—C23 | −19.4 (4) |
C7—C7A—C8—C9 | 178.4 (3) | N1—C2—C22—S21 | −79.1 (3) |
C11A—C7A—C8—C9 | −0.5 (4) | C3—C2—C22—S21 | 164.25 (19) |
C7A—C8—C9—C10 | 0.6 (5) | C25—S21—C22—C23 | 0.0 (2) |
C8—C9—C10—C11 | −0.6 (5) | C25—S21—C22—C2 | 177.1 (2) |
C9—C10—C11—C11A | 0.4 (4) | C2—C22—C23—C24 | −177.3 (3) |
C10—C11—C11A—C7A | −0.3 (4) | S21—C22—C23—C24 | −0.6 (3) |
C10—C11—C11A—C11B | −179.0 (3) | C22—C23—C24—C25 | 1.2 (4) |
C8—C7A—C11A—C11 | 0.4 (4) | C23—C24—C25—C26 | 178.3 (3) |
C7—C7A—C11A—C11 | −178.5 (3) | C23—C24—C25—S21 | −1.1 (3) |
C8—C7A—C11A—C11B | 179.1 (3) | C22—S21—C25—C24 | 0.6 (2) |
C7—C7A—C11A—C11B | 0.2 (4) | C22—S21—C25—C26 | −178.8 (3) |
C6—C5A—C11B—C11A | 0.3 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···N1i | 0.99 | 2.59 | 3.545 (4) | 163 |
C5—H5B···O14i | 0.99 | 2.50 | 3.436 (3) | 157 |
Symmetry code: (i) x, y−1, z. |
(III) (
2RS,4
SR)-2-(5-bromothiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-
b]azepine
top
Crystal data top
C18H14BrNOS | F(000) = 1504 |
Mr = 372.27 | Dx = 1.609 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 6933 reflections |
a = 15.316 (2) Å | θ = 2.7–27.5° |
b = 9.9230 (18) Å | µ = 2.81 mm−1 |
c = 20.225 (3) Å | T = 120 K |
V = 3073.8 (8) Å3 | Needle, pale yellow |
Z = 8 | 0.40 × 0.14 × 0.12 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 6933 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 5427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ & ω scans | h = −17→19 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→12 |
Tmin = 0.399, Tmax = 0.729 | l = −26→25 |
27630 measured reflections | |
Refinement top
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0341P)2 + 0.3624P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
6932 reflections | Δρmax = 0.87 e Å−3 |
398 parameters | Δρmin = −0.43 e Å−3 |
1 restraint | Absolute structure: Flack (1983); this is not a conventional Flack x parameter but a twin
fraction, calculated using TWIN and BASF |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.663 (9) |
Crystal data top
C18H14BrNOS | V = 3073.8 (8) Å3 |
Mr = 372.27 | Z = 8 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 15.316 (2) Å | µ = 2.81 mm−1 |
b = 9.9230 (18) Å | T = 120 K |
c = 20.225 (3) Å | 0.40 × 0.14 × 0.12 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 6933 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5427 reflections with I > 2σ(I) |
Tmin = 0.399, Tmax = 0.729 | Rint = 0.049 |
27630 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.076 | Δρmax = 0.87 e Å−3 |
S = 1.03 | Δρmin = −0.43 e Å−3 |
6932 reflections | Absolute structure: Flack (1983); this is not a conventional Flack x parameter but a twin
fraction, calculated using TWIN and BASF |
398 parameters | Absolute structure parameter: 0.663 (9) |
1 restraint | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N11 | 0.3118 (2) | 0.8001 (4) | 0.43537 (14) | 0.0153 (7) | |
C12 | 0.2192 (2) | 0.7982 (5) | 0.41230 (19) | 0.0175 (8) | |
H12 | 0.2152 | 0.7512 | 0.3687 | 0.021* | |
C13 | 0.1972 (2) | 0.9498 (4) | 0.4036 (2) | 0.0204 (9) | |
H13A | 0.1991 | 0.9763 | 0.3564 | 0.025* | |
H13B | 0.1388 | 0.9710 | 0.4217 | 0.025* | |
C14 | 0.2696 (3) | 1.0206 (4) | 0.4433 (2) | 0.0214 (9) | |
H14 | 0.2446 | 1.0908 | 0.4733 | 0.026* | |
C15 | 0.3417 (3) | 1.0795 (4) | 0.4003 (2) | 0.0207 (9) | |
H15A | 0.3162 | 1.1420 | 0.3673 | 0.025* | |
H15B | 0.3834 | 1.1306 | 0.4280 | 0.025* | |
C15A | 0.3886 (3) | 0.9661 (5) | 0.3654 (2) | 0.0181 (11) | |
C16 | 0.4511 (3) | 0.9914 (5) | 0.3155 (2) | 0.0205 (11) | |
H16 | 0.4646 | 1.0820 | 0.3045 | 0.025* | |
C17 | 0.4926 (3) | 0.8896 (5) | 0.2826 (2) | 0.0227 (12) | |
H17 | 0.5339 | 0.9107 | 0.2492 | 0.027* | |
C17A | 0.4749 (4) | 0.7534 (4) | 0.2977 (4) | 0.0164 (16) | |
C18 | 0.5162 (3) | 0.6442 (5) | 0.2656 (2) | 0.0212 (12) | |
H18 | 0.5574 | 0.6620 | 0.2316 | 0.025* | |
C19 | 0.4986 (3) | 0.5140 (5) | 0.2823 (2) | 0.0254 (10) | |
H19 | 0.5269 | 0.4422 | 0.2597 | 0.030* | |
C110 | 0.4385 (3) | 0.4862 (6) | 0.3331 (2) | 0.0256 (12) | |
H110 | 0.4262 | 0.3953 | 0.3445 | 0.031* | |
C111 | 0.3975 (3) | 0.5884 (5) | 0.3661 (2) | 0.0186 (11) | |
H111 | 0.3580 | 0.5670 | 0.4008 | 0.022* | |
C11A | 0.4122 (4) | 0.7248 (5) | 0.3501 (3) | 0.0143 (10) | |
C11B | 0.3714 (2) | 0.8345 (5) | 0.38212 (18) | 0.0157 (9) | |
O114 | 0.30923 (19) | 0.9120 (2) | 0.48113 (12) | 0.0187 (6) | |
S121 | 0.18004 (11) | 0.73901 (13) | 0.54603 (10) | 0.0205 (4) | |
C122 | 0.1610 (4) | 0.7293 (5) | 0.4618 (3) | 0.0160 (12) | |
C123 | 0.0858 (3) | 0.6624 (4) | 0.44928 (19) | 0.0192 (9) | |
H123 | 0.0647 | 0.6469 | 0.4058 | 0.023* | |
C124 | 0.0415 (3) | 0.6178 (4) | 0.5061 (2) | 0.0181 (8) | |
H124 | −0.0121 | 0.5698 | 0.5056 | 0.022* | |
C125 | 0.0853 (3) | 0.6523 (4) | 0.56138 (19) | 0.0197 (9) | |
Br15 | 0.05695 (3) | 0.61051 (5) | 0.65017 (2) | 0.02996 (11) | |
N21 | 0.5651 (2) | 0.6960 (4) | 0.04523 (14) | 0.0165 (7) | |
C22 | 0.4727 (2) | 0.6961 (4) | 0.06898 (19) | 0.0154 (8) | |
H22 | 0.4688 | 0.7434 | 0.1125 | 0.018* | |
C23 | 0.4509 (3) | 0.5424 (4) | 0.0780 (2) | 0.0218 (9) | |
H23A | 0.4514 | 0.5167 | 0.1253 | 0.026* | |
H23B | 0.3931 | 0.5203 | 0.0589 | 0.026* | |
C24 | 0.5243 (3) | 0.4724 (4) | 0.0401 (2) | 0.0227 (9) | |
H24 | 0.5005 | 0.3999 | 0.0108 | 0.027* | |
C25 | 0.5956 (3) | 0.4179 (4) | 0.0844 (2) | 0.0257 (10) | |
H25A | 0.5700 | 0.3573 | 0.1182 | 0.031* | |
H25B | 0.6379 | 0.3654 | 0.0579 | 0.031* | |
C25A | 0.6415 (3) | 0.5343 (5) | 0.1179 (3) | 0.0189 (11) | |
C26 | 0.7037 (3) | 0.5115 (5) | 0.1690 (2) | 0.0245 (12) | |
H26 | 0.7171 | 0.4216 | 0.1816 | 0.029* | |
C27 | 0.7446 (3) | 0.6163 (6) | 0.2005 (2) | 0.0225 (12) | |
H27 | 0.7844 | 0.5984 | 0.2354 | 0.027* | |
C27A | 0.7277 (4) | 0.7510 (4) | 0.1811 (4) | 0.0197 (17) | |
C28 | 0.7719 (3) | 0.8637 (6) | 0.2093 (2) | 0.0247 (12) | |
H28 | 0.8133 | 0.8492 | 0.2434 | 0.030* | |
C29 | 0.7559 (3) | 0.9910 (5) | 0.1883 (2) | 0.0250 (10) | |
H29 | 0.7872 | 1.0641 | 0.2073 | 0.030* | |
C210 | 0.6940 (3) | 1.0160 (5) | 0.1391 (2) | 0.0200 (10) | |
H210 | 0.6823 | 1.1060 | 0.1257 | 0.024* | |
C211 | 0.6502 (3) | 0.9119 (5) | 0.1101 (2) | 0.0160 (10) | |
H211 | 0.6084 | 0.9297 | 0.0765 | 0.019* | |
C21A | 0.6669 (4) | 0.7764 (5) | 0.1302 (3) | 0.0179 (12) | |
C21B | 0.6246 (3) | 0.6649 (5) | 0.09965 (19) | 0.0176 (9) | |
O214 | 0.56441 (19) | 0.5798 (3) | 0.00080 (13) | 0.0199 (6) | |
S221 | 0.43371 (10) | 0.75414 (10) | −0.06499 (10) | 0.0179 (4) | |
C222 | 0.4145 (4) | 0.7632 (4) | 0.0199 (4) | 0.0142 (13) | |
C223 | 0.3388 (3) | 0.8307 (4) | 0.03218 (19) | 0.0177 (9) | |
H223 | 0.3175 | 0.8463 | 0.0756 | 0.021* | |
C224 | 0.2943 (3) | 0.8759 (4) | −0.0258 (2) | 0.0214 (9) | |
H224 | 0.2402 | 0.9229 | −0.0257 | 0.026* | |
C225 | 0.3393 (2) | 0.8429 (4) | −0.08085 (19) | 0.0193 (9) | |
Br25 | 0.31015 (3) | 0.88673 (5) | −0.16844 (2) | 0.02968 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N11 | 0.0142 (16) | 0.0169 (19) | 0.0149 (16) | 0.0057 (16) | 0.0001 (15) | −0.0023 (14) |
C12 | 0.012 (2) | 0.025 (2) | 0.015 (2) | 0.001 (2) | 0.0002 (16) | −0.0018 (19) |
C13 | 0.017 (2) | 0.023 (2) | 0.021 (2) | 0.0014 (17) | −0.0001 (16) | 0.0055 (19) |
C14 | 0.021 (2) | 0.016 (2) | 0.027 (2) | 0.0040 (18) | 0.0054 (18) | −0.0012 (18) |
C15 | 0.018 (2) | 0.018 (2) | 0.026 (2) | −0.0005 (16) | 0.0004 (17) | −0.0026 (17) |
C15A | 0.018 (2) | 0.018 (3) | 0.018 (2) | −0.001 (2) | −0.0035 (18) | 0.004 (2) |
C16 | 0.023 (2) | 0.020 (3) | 0.018 (2) | −0.005 (2) | −0.0046 (19) | 0.0035 (19) |
C17 | 0.020 (2) | 0.033 (3) | 0.015 (2) | −0.005 (2) | −0.0017 (19) | 0.008 (2) |
C17A | 0.011 (3) | 0.025 (4) | 0.013 (3) | −0.0021 (16) | −0.002 (3) | 0.0021 (15) |
C18 | 0.014 (2) | 0.031 (3) | 0.019 (2) | −0.003 (2) | 0.0041 (18) | −0.002 (2) |
C19 | 0.024 (2) | 0.029 (3) | 0.023 (2) | 0.004 (2) | 0.0010 (18) | −0.0059 (19) |
C110 | 0.022 (2) | 0.024 (3) | 0.031 (3) | 0.003 (2) | −0.008 (2) | −0.001 (2) |
C111 | 0.014 (2) | 0.026 (3) | 0.016 (2) | 0.000 (2) | −0.0013 (17) | 0.006 (2) |
C11A | 0.010 (2) | 0.026 (2) | 0.007 (2) | −0.003 (2) | −0.0032 (18) | 0.006 (2) |
C11B | 0.0081 (19) | 0.025 (2) | 0.0144 (19) | −0.0029 (19) | −0.0020 (16) | −0.0008 (19) |
O114 | 0.0188 (13) | 0.0214 (15) | 0.0161 (13) | 0.0029 (13) | −0.0018 (12) | −0.0032 (11) |
S121 | 0.0178 (8) | 0.0282 (10) | 0.0157 (9) | −0.0035 (4) | −0.0020 (7) | 0.0006 (5) |
C122 | 0.017 (3) | 0.016 (2) | 0.014 (3) | 0.001 (2) | 0.001 (2) | 0.003 (2) |
C123 | 0.0154 (19) | 0.024 (2) | 0.018 (2) | −0.0012 (18) | −0.0045 (17) | −0.0028 (18) |
C124 | 0.0126 (17) | 0.019 (2) | 0.023 (2) | −0.0046 (17) | −0.0037 (17) | 0.0023 (19) |
C125 | 0.019 (2) | 0.018 (2) | 0.022 (2) | 0.0039 (18) | 0.0030 (17) | 0.0045 (17) |
Br15 | 0.0247 (2) | 0.0440 (3) | 0.02112 (18) | −0.0014 (2) | 0.00419 (18) | 0.0102 (3) |
N21 | 0.0124 (16) | 0.023 (2) | 0.0136 (15) | 0.0050 (16) | −0.0034 (14) | −0.0046 (15) |
C22 | 0.013 (2) | 0.015 (2) | 0.018 (2) | 0.0003 (19) | 0.0004 (16) | 0.0010 (19) |
C23 | 0.019 (2) | 0.018 (2) | 0.029 (2) | −0.0042 (17) | −0.0009 (17) | 0.001 (2) |
C24 | 0.022 (2) | 0.019 (2) | 0.028 (2) | −0.0034 (18) | 0.0021 (18) | 0.0010 (19) |
C25 | 0.020 (2) | 0.025 (3) | 0.032 (2) | 0.0027 (18) | 0.0037 (19) | 0.0028 (19) |
C25A | 0.015 (2) | 0.023 (3) | 0.018 (2) | 0.000 (2) | 0.0044 (18) | −0.003 (2) |
C26 | 0.020 (2) | 0.027 (3) | 0.026 (3) | 0.009 (2) | 0.006 (2) | 0.014 (2) |
C27 | 0.013 (2) | 0.037 (3) | 0.017 (2) | 0.004 (2) | −0.0024 (18) | 0.001 (2) |
C27A | 0.014 (3) | 0.032 (5) | 0.013 (3) | 0.0029 (17) | 0.005 (3) | 0.0008 (16) |
C28 | 0.017 (2) | 0.041 (3) | 0.016 (2) | −0.004 (2) | 0.0022 (18) | −0.005 (2) |
C29 | 0.021 (2) | 0.034 (3) | 0.020 (2) | −0.006 (2) | 0.0031 (18) | −0.0085 (19) |
C210 | 0.020 (2) | 0.022 (2) | 0.018 (2) | −0.0031 (19) | 0.0052 (19) | 0.0010 (19) |
C211 | 0.015 (2) | 0.020 (3) | 0.013 (2) | −0.001 (2) | 0.0017 (17) | 0.001 (2) |
C21A | 0.011 (2) | 0.025 (2) | 0.018 (3) | −0.006 (2) | 0.0020 (19) | −0.004 (2) |
C21B | 0.015 (2) | 0.025 (2) | 0.013 (2) | 0.001 (2) | 0.0038 (17) | 0.0046 (19) |
O214 | 0.0219 (14) | 0.0186 (15) | 0.0191 (13) | 0.0007 (13) | 0.0013 (13) | −0.0067 (11) |
S221 | 0.0148 (8) | 0.0233 (9) | 0.0156 (9) | 0.0017 (4) | −0.0028 (7) | 0.0004 (4) |
C222 | 0.012 (2) | 0.014 (2) | 0.016 (3) | −0.0038 (17) | 0.001 (2) | −0.0014 (17) |
C223 | 0.017 (2) | 0.017 (2) | 0.018 (2) | −0.0042 (18) | 0.0011 (17) | 0.0025 (18) |
C224 | 0.0164 (18) | 0.020 (2) | 0.028 (2) | −0.0078 (18) | −0.0040 (18) | 0.0033 (19) |
C225 | 0.018 (2) | 0.021 (2) | 0.0192 (19) | −0.0006 (18) | −0.0014 (18) | 0.0060 (18) |
Br25 | 0.0232 (2) | 0.0436 (3) | 0.02227 (18) | −0.0012 (2) | −0.00527 (17) | 0.0107 (3) |
N11 | 0.0142 (16) | 0.0169 (19) | 0.0149 (16) | 0.0057 (16) | 0.0001 (15) | −0.0023 (14) |
C12 | 0.012 (2) | 0.025 (2) | 0.015 (2) | 0.001 (2) | 0.0002 (16) | −0.0018 (19) |
C13 | 0.017 (2) | 0.023 (2) | 0.021 (2) | 0.0014 (17) | −0.0001 (16) | 0.0055 (19) |
C14 | 0.021 (2) | 0.016 (2) | 0.027 (2) | 0.0040 (18) | 0.0054 (18) | −0.0012 (18) |
C15 | 0.018 (2) | 0.018 (2) | 0.026 (2) | −0.0005 (16) | 0.0004 (17) | −0.0026 (17) |
C15A | 0.018 (2) | 0.018 (3) | 0.018 (2) | −0.001 (2) | −0.0035 (18) | 0.004 (2) |
C16 | 0.023 (2) | 0.020 (3) | 0.018 (2) | −0.005 (2) | −0.0046 (19) | 0.0035 (19) |
C17 | 0.020 (2) | 0.033 (3) | 0.015 (2) | −0.005 (2) | −0.0017 (19) | 0.008 (2) |
C17A | 0.011 (3) | 0.025 (4) | 0.013 (3) | −0.0021 (16) | −0.002 (3) | 0.0021 (15) |
C18 | 0.014 (2) | 0.031 (3) | 0.019 (2) | −0.003 (2) | 0.0041 (18) | −0.002 (2) |
C19 | 0.024 (2) | 0.029 (3) | 0.023 (2) | 0.004 (2) | 0.0010 (18) | −0.0059 (19) |
C110 | 0.022 (2) | 0.024 (3) | 0.031 (3) | 0.003 (2) | −0.008 (2) | −0.001 (2) |
C111 | 0.014 (2) | 0.026 (3) | 0.016 (2) | 0.000 (2) | −0.0013 (17) | 0.006 (2) |
C11A | 0.010 (2) | 0.026 (2) | 0.007 (2) | −0.003 (2) | −0.0032 (18) | 0.006 (2) |
C11B | 0.0081 (19) | 0.025 (2) | 0.0144 (19) | −0.0029 (19) | −0.0020 (16) | −0.0008 (19) |
O114 | 0.0188 (13) | 0.0214 (15) | 0.0161 (13) | 0.0029 (13) | −0.0018 (12) | −0.0032 (11) |
S121 | 0.0178 (8) | 0.0282 (10) | 0.0157 (9) | −0.0035 (4) | −0.0020 (7) | 0.0006 (5) |
C122 | 0.017 (3) | 0.016 (2) | 0.014 (3) | 0.001 (2) | 0.001 (2) | 0.003 (2) |
C123 | 0.0154 (19) | 0.024 (2) | 0.018 (2) | −0.0012 (18) | −0.0045 (17) | −0.0028 (18) |
C124 | 0.0126 (17) | 0.019 (2) | 0.023 (2) | −0.0046 (17) | −0.0037 (17) | 0.0023 (19) |
C125 | 0.019 (2) | 0.018 (2) | 0.022 (2) | 0.0039 (18) | 0.0030 (17) | 0.0045 (17) |
Br15 | 0.0247 (2) | 0.0440 (3) | 0.02112 (18) | −0.0014 (2) | 0.00419 (18) | 0.0102 (3) |
N21 | 0.0124 (16) | 0.023 (2) | 0.0136 (15) | 0.0050 (16) | −0.0034 (14) | −0.0046 (15) |
C22 | 0.013 (2) | 0.015 (2) | 0.018 (2) | 0.0003 (19) | 0.0004 (16) | 0.0010 (19) |
C23 | 0.019 (2) | 0.018 (2) | 0.029 (2) | −0.0042 (17) | −0.0009 (17) | 0.001 (2) |
C24 | 0.022 (2) | 0.019 (2) | 0.028 (2) | −0.0034 (18) | 0.0021 (18) | 0.0010 (19) |
C25 | 0.020 (2) | 0.025 (3) | 0.032 (2) | 0.0027 (18) | 0.0037 (19) | 0.0028 (19) |
C25A | 0.015 (2) | 0.023 (3) | 0.018 (2) | 0.000 (2) | 0.0044 (18) | −0.003 (2) |
C26 | 0.020 (2) | 0.027 (3) | 0.026 (3) | 0.009 (2) | 0.006 (2) | 0.014 (2) |
C27 | 0.013 (2) | 0.037 (3) | 0.017 (2) | 0.004 (2) | −0.0024 (18) | 0.001 (2) |
C27A | 0.014 (3) | 0.032 (5) | 0.013 (3) | 0.0029 (17) | 0.005 (3) | 0.0008 (16) |
C28 | 0.017 (2) | 0.041 (3) | 0.016 (2) | −0.004 (2) | 0.0022 (18) | −0.005 (2) |
C29 | 0.021 (2) | 0.034 (3) | 0.020 (2) | −0.006 (2) | 0.0031 (18) | −0.0085 (19) |
C210 | 0.020 (2) | 0.022 (2) | 0.018 (2) | −0.0031 (19) | 0.0052 (19) | 0.0010 (19) |
C211 | 0.015 (2) | 0.020 (3) | 0.013 (2) | −0.001 (2) | 0.0017 (17) | 0.001 (2) |
C21A | 0.011 (2) | 0.025 (2) | 0.018 (3) | −0.006 (2) | 0.0020 (19) | −0.004 (2) |
C21B | 0.015 (2) | 0.025 (2) | 0.013 (2) | 0.001 (2) | 0.0038 (17) | 0.0046 (19) |
O214 | 0.0219 (14) | 0.0186 (15) | 0.0191 (13) | 0.0007 (13) | 0.0013 (13) | −0.0067 (11) |
S221 | 0.0148 (8) | 0.0233 (9) | 0.0156 (9) | 0.0017 (4) | −0.0028 (7) | 0.0004 (4) |
C222 | 0.012 (2) | 0.014 (2) | 0.016 (3) | −0.0038 (17) | 0.001 (2) | −0.0014 (17) |
C223 | 0.017 (2) | 0.017 (2) | 0.018 (2) | −0.0042 (18) | 0.0011 (17) | 0.0025 (18) |
C224 | 0.0164 (18) | 0.020 (2) | 0.028 (2) | −0.0078 (18) | −0.0040 (18) | 0.0033 (19) |
C225 | 0.018 (2) | 0.021 (2) | 0.0192 (19) | −0.0006 (18) | −0.0014 (18) | 0.0060 (18) |
Br25 | 0.0232 (2) | 0.0436 (3) | 0.02227 (18) | −0.0012 (2) | −0.00527 (17) | 0.0107 (3) |
Geometric parameters (Å, º) top
N11—O114 | 1.447 (4) | N21—O214 | 1.461 (4) |
N11—C11B | 1.453 (5) | N21—C21B | 1.462 (5) |
N11—C12 | 1.493 (5) | N21—C22 | 1.493 (5) |
C12—C122 | 1.505 (7) | C22—C222 | 1.492 (8) |
C12—C13 | 1.551 (6) | C22—C23 | 1.571 (6) |
C12—H12 | 1.0000 | C22—H22 | 1.0000 |
C13—C14 | 1.539 (5) | C23—C24 | 1.528 (6) |
C13—H13A | 0.9900 | C23—H23A | 0.9900 |
C13—H13B | 0.9900 | C23—H23B | 0.9900 |
C14—O114 | 1.453 (5) | C24—O214 | 1.464 (5) |
C14—C15 | 1.523 (5) | C24—C25 | 1.513 (6) |
C14—H14 | 1.0000 | C24—H24 | 1.0000 |
C15—C15A | 1.510 (6) | C25—C25A | 1.512 (7) |
C15—H15A | 0.9900 | C25—H25A | 0.9900 |
C15—H15B | 0.9900 | C25—H25B | 0.9900 |
C15A—C11B | 1.374 (6) | C25A—C21B | 1.372 (6) |
C15A—C16 | 1.414 (7) | C25A—C26 | 1.424 (7) |
C16—C17 | 1.366 (7) | C26—C27 | 1.370 (7) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C17A | 1.412 (6) | C27—C27A | 1.417 (7) |
C17—H17 | 0.9500 | C27—H27 | 0.9500 |
C17A—C18 | 1.413 (7) | C27A—C21A | 1.413 (9) |
C17A—C11A | 1.457 (9) | C27A—C28 | 1.425 (7) |
C18—C19 | 1.362 (7) | C28—C29 | 1.355 (7) |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C19—C110 | 1.406 (6) | C29—C210 | 1.397 (6) |
C19—H19 | 0.9500 | C29—H29 | 0.9500 |
C110—C111 | 1.368 (7) | C210—C211 | 1.364 (6) |
C110—H110 | 0.9500 | C210—H210 | 0.9500 |
C111—C11A | 1.410 (7) | C211—C21A | 1.428 (7) |
C111—H111 | 0.9500 | C211—H211 | 0.9500 |
C11A—C11B | 1.414 (6) | C21A—C21B | 1.422 (6) |
S121—C125 | 1.715 (4) | S221—C225 | 1.723 (4) |
S121—C122 | 1.730 (7) | S221—C222 | 1.744 (7) |
C122—C123 | 1.353 (7) | C222—C223 | 1.361 (7) |
C123—C124 | 1.406 (6) | C223—C224 | 1.430 (6) |
C123—H123 | 0.9500 | C223—H223 | 0.9500 |
C124—C125 | 1.348 (5) | C224—C225 | 1.349 (6) |
C124—H124 | 0.9500 | C224—H224 | 0.9500 |
C125—Br15 | 1.893 (4) | C225—Br25 | 1.878 (4) |
| | | |
O114—N11—C11B | 108.1 (3) | O214—N21—C21B | 107.5 (3) |
O114—N11—C12 | 100.6 (3) | O214—N21—C22 | 101.0 (3) |
C11B—N11—C12 | 111.6 (3) | C21B—N21—C22 | 110.4 (3) |
N11—C12—C122 | 111.1 (4) | C222—C22—N21 | 110.6 (4) |
N11—C12—C13 | 103.3 (3) | C222—C22—C23 | 112.5 (3) |
C122—C12—C13 | 112.8 (4) | N21—C22—C23 | 103.8 (3) |
N11—C12—H12 | 109.8 | C222—C22—H22 | 109.9 |
C122—C12—H12 | 109.8 | N21—C22—H22 | 109.9 |
C13—C12—H12 | 109.8 | C23—C22—H22 | 109.9 |
C14—C13—C12 | 103.1 (3) | C24—C23—C22 | 103.1 (3) |
C14—C13—H13A | 111.1 | C24—C23—H23A | 111.2 |
C12—C13—H13A | 111.1 | C22—C23—H23A | 111.2 |
C14—C13—H13B | 111.1 | C24—C23—H23B | 111.2 |
C12—C13—H13B | 111.1 | C22—C23—H23B | 111.2 |
H13A—C13—H13B | 109.1 | H23A—C23—H23B | 109.1 |
O114—C14—C15 | 106.4 (3) | O214—C24—C25 | 106.2 (3) |
O114—C14—C13 | 103.7 (3) | O214—C24—C23 | 104.5 (3) |
C15—C14—C13 | 113.5 (3) | C25—C24—C23 | 113.3 (4) |
O114—C14—H14 | 111.0 | O214—C24—H24 | 110.8 |
C15—C14—H14 | 111.0 | C25—C24—H24 | 110.8 |
C13—C14—H14 | 111.0 | C23—C24—H24 | 110.8 |
C15A—C15—C14 | 109.0 (3) | C25A—C25—C24 | 109.1 (4) |
C15A—C15—H15A | 109.9 | C25A—C25—H25A | 109.9 |
C14—C15—H15A | 109.9 | C24—C25—H25A | 109.9 |
C15A—C15—H15B | 109.9 | C25A—C25—H25B | 109.9 |
C14—C15—H15B | 109.9 | C24—C25—H25B | 109.9 |
H15A—C15—H15B | 108.3 | H25A—C25—H25B | 108.3 |
C11B—C15A—C16 | 118.3 (4) | C21B—C25A—C26 | 118.1 (4) |
C11B—C15A—C15 | 120.1 (4) | C21B—C25A—C25 | 120.9 (4) |
C16—C15A—C15 | 121.6 (4) | C26—C25A—C25 | 120.9 (4) |
C17—C16—C15A | 122.1 (5) | C27—C26—C25A | 121.5 (5) |
C17—C16—H16 | 119.0 | C27—C26—H26 | 119.3 |
C15A—C16—H16 | 119.0 | C25A—C26—H26 | 119.3 |
C16—C17—C17A | 120.9 (5) | C26—C27—C27A | 120.3 (5) |
C16—C17—H17 | 119.5 | C26—C27—H27 | 119.8 |
C17A—C17—H17 | 119.5 | C27A—C27—H27 | 119.8 |
C17—C17A—C18 | 123.3 (6) | C21A—C27A—C27 | 119.3 (5) |
C17—C17A—C11A | 118.0 (5) | C21A—C27A—C28 | 117.7 (4) |
C18—C17A—C11A | 118.6 (4) | C27—C27A—C28 | 123.0 (6) |
C19—C18—C17A | 121.7 (4) | C29—C28—C27A | 121.5 (5) |
C19—C18—H18 | 119.2 | C29—C28—H28 | 119.3 |
C17A—C18—H18 | 119.2 | C27A—C28—H28 | 119.3 |
C18—C19—C110 | 119.8 (5) | C28—C29—C210 | 120.7 (5) |
C18—C19—H19 | 120.1 | C28—C29—H29 | 119.7 |
C110—C19—H19 | 120.1 | C210—C29—H29 | 119.7 |
C111—C110—C19 | 120.8 (5) | C211—C210—C29 | 120.4 (5) |
C111—C110—H110 | 119.6 | C211—C210—H210 | 119.8 |
C19—C110—H110 | 119.6 | C29—C210—H210 | 119.8 |
C110—C111—C11A | 121.6 (5) | C210—C211—C21A | 120.2 (5) |
C110—C111—H111 | 119.2 | C210—C211—H211 | 119.9 |
C11A—C111—H111 | 119.2 | C21A—C211—H211 | 119.9 |
C111—C11A—C11B | 124.2 (5) | C27A—C21A—C21B | 118.6 (4) |
C111—C11A—C17A | 117.4 (4) | C27A—C21A—C211 | 119.6 (4) |
C11B—C11A—C17A | 118.3 (4) | C21B—C21A—C211 | 121.9 (5) |
C15A—C11B—C11A | 122.3 (4) | C25A—C21B—C21A | 122.2 (4) |
C15A—C11B—N11 | 121.8 (4) | C25A—C21B—N21 | 121.2 (4) |
C11A—C11B—N11 | 115.9 (4) | C21A—C21B—N21 | 116.5 (4) |
N11—O114—C14 | 104.1 (3) | N21—O214—C24 | 104.1 (3) |
C125—S121—C122 | 90.4 (3) | C225—S221—C222 | 90.9 (3) |
C123—C122—C12 | 127.0 (5) | C223—C222—C22 | 127.4 (6) |
C123—C122—S121 | 110.8 (4) | C223—C222—S221 | 110.4 (5) |
C12—C122—S121 | 122.0 (4) | C22—C222—S221 | 122.1 (4) |
C122—C123—C124 | 114.3 (4) | C222—C223—C224 | 114.3 (4) |
C122—C123—H123 | 122.8 | C222—C223—H223 | 122.9 |
C124—C123—H123 | 122.8 | C224—C223—H223 | 122.9 |
C125—C124—C123 | 111.0 (3) | C225—C224—C223 | 110.9 (4) |
C125—C124—H124 | 124.5 | C225—C224—H224 | 124.6 |
C123—C124—H124 | 124.5 | C223—C224—H224 | 124.6 |
C124—C125—S121 | 113.5 (3) | C224—C225—S221 | 113.5 (3) |
C124—C125—Br15 | 128.1 (3) | C224—C225—Br25 | 126.9 (3) |
S121—C125—Br15 | 118.4 (2) | S221—C225—Br25 | 119.6 (2) |
| | | |
O114—N11—C12—C122 | −80.0 (4) | O214—N21—C22—C222 | −82.0 (4) |
C11B—N11—C12—C122 | 165.6 (4) | C21B—N21—C22—C222 | 164.5 (4) |
O114—N11—C12—C13 | 41.2 (3) | O214—N21—C22—C23 | 39.0 (3) |
C11B—N11—C12—C13 | −73.3 (4) | C21B—N21—C22—C23 | −74.6 (4) |
N11—C12—C13—C14 | −17.2 (4) | C222—C22—C23—C24 | 104.3 (4) |
C122—C12—C13—C14 | 102.8 (4) | N21—C22—C23—C24 | −15.3 (4) |
C12—C13—C14—O114 | −12.8 (3) | C22—C23—C24—O214 | −14.1 (4) |
C12—C13—C14—C15 | 102.2 (4) | C22—C23—C24—C25 | 101.1 (4) |
O114—C14—C15—C15A | 48.8 (4) | O214—C24—C25—C25A | 48.6 (4) |
C13—C14—C15—C15A | −64.6 (4) | C23—C24—C25—C25A | −65.5 (5) |
C14—C15—C15A—C11B | −8.8 (5) | C24—C25—C25A—C21B | −8.6 (6) |
C14—C15—C15A—C16 | 171.6 (4) | C24—C25—C25A—C26 | 171.6 (4) |
C11B—C15A—C16—C17 | 1.8 (6) | C21B—C25A—C26—C27 | 1.3 (7) |
C15—C15A—C16—C17 | −178.6 (4) | C25—C25A—C26—C27 | −178.8 (4) |
C15A—C16—C17—C17A | −0.4 (7) | C25A—C26—C27—C27A | −2.0 (7) |
C16—C17—C17A—C18 | −179.5 (5) | C26—C27—C27A—C21A | 1.5 (9) |
C16—C17—C17A—C11A | −1.1 (8) | C26—C27—C27A—C28 | −176.3 (5) |
C17—C17A—C18—C19 | 178.8 (5) | C21A—C27A—C28—C29 | 0.3 (8) |
C11A—C17A—C18—C19 | 0.4 (9) | C27—C27A—C28—C29 | 178.1 (5) |
C17A—C18—C19—C110 | −0.7 (7) | C27A—C28—C29—C210 | 1.4 (7) |
C18—C19—C110—C111 | −0.2 (7) | C28—C29—C210—C211 | −1.8 (6) |
C19—C110—C111—C11A | 1.3 (7) | C29—C210—C211—C21A | 0.4 (7) |
C110—C111—C11A—C11B | 179.5 (5) | C27—C27A—C21A—C21B | −0.3 (9) |
C110—C111—C11A—C17A | −1.5 (8) | C28—C27A—C21A—C21B | 177.6 (5) |
C17—C17A—C11A—C111 | −177.8 (5) | C27—C27A—C21A—C211 | −179.5 (5) |
C18—C17A—C11A—C111 | 0.7 (9) | C28—C27A—C21A—C211 | −1.7 (9) |
C17—C17A—C11A—C11B | 1.2 (8) | C210—C211—C21A—C27A | 1.3 (8) |
C18—C17A—C11A—C11B | 179.7 (5) | C210—C211—C21A—C21B | −177.9 (4) |
C16—C15A—C11B—C11A | −1.6 (6) | C26—C25A—C21B—C21A | −0.1 (7) |
C15—C15A—C11B—C11A | 178.7 (4) | C25—C25A—C21B—C21A | −179.9 (4) |
C16—C15A—C11B—N11 | 176.5 (4) | C26—C25A—C21B—N21 | 176.8 (3) |
C15—C15A—C11B—N11 | −3.2 (6) | C25—C25A—C21B—N21 | −3.1 (6) |
C111—C11A—C11B—C15A | 179.1 (5) | C27A—C21A—C21B—C25A | −0.4 (8) |
C17A—C11A—C11B—C15A | 0.2 (7) | C211—C21A—C21B—C25A | 178.8 (5) |
C111—C11A—C11B—N11 | 0.9 (7) | C27A—C21A—C21B—N21 | −177.4 (5) |
C17A—C11A—C11B—N11 | −178.0 (5) | C211—C21A—C21B—N21 | 1.8 (7) |
O114—N11—C11B—C15A | −25.3 (5) | O214—N21—C21B—C25A | −25.7 (5) |
C12—N11—C11B—C15A | 84.4 (4) | C22—N21—C21B—C25A | 83.7 (5) |
O114—N11—C11B—C11A | 152.9 (4) | O214—N21—C21B—C21A | 151.3 (4) |
C12—N11—C11B—C11A | −97.4 (4) | C22—N21—C21B—C21A | −99.3 (4) |
C11B—N11—O114—C14 | 65.8 (3) | C21B—N21—O214—C24 | 66.2 (3) |
C12—N11—O114—C14 | −51.3 (3) | C22—N21—O214—C24 | −49.5 (3) |
C15—C14—O114—N11 | −80.1 (3) | C25—C24—O214—N21 | −80.4 (4) |
C13—C14—O114—N11 | 39.9 (3) | C23—C24—O214—N21 | 39.7 (4) |
N11—C12—C122—C123 | −151.7 (5) | N21—C22—C222—C223 | −151.1 (4) |
C13—C12—C122—C123 | 92.9 (6) | C23—C22—C222—C223 | 93.2 (5) |
N11—C12—C122—S121 | 33.6 (6) | N21—C22—C222—S221 | 33.2 (5) |
C13—C12—C122—S121 | −81.8 (5) | C23—C22—C222—S221 | −82.4 (4) |
C125—S121—C122—C123 | −0.1 (4) | C225—S221—C222—C223 | 0.5 (4) |
C125—S121—C122—C12 | 175.4 (4) | C225—S221—C222—C22 | 176.8 (4) |
C12—C122—C123—C124 | −175.0 (4) | C22—C222—C223—C224 | −175.7 (4) |
S121—C122—C123—C124 | 0.2 (6) | S221—C222—C223—C224 | 0.3 (5) |
C122—C123—C124—C125 | −0.3 (6) | C222—C223—C224—C225 | −1.2 (5) |
C123—C124—C125—S121 | 0.2 (5) | C223—C224—C225—S221 | 1.5 (4) |
C123—C124—C125—Br15 | −177.2 (3) | C223—C224—C225—Br25 | −177.2 (3) |
C122—S121—C125—C124 | 0.0 (3) | C222—S221—C225—C224 | −1.2 (3) |
C122—S121—C125—Br15 | 177.6 (3) | C222—S221—C225—Br25 | 177.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Cg3i | 1.00 | 2.75 | 3.616 (5) | 143 |
C24—H24···Cg4ii | 1.00 | 2.77 | 3.632 (5) | 145 |
C18—H18···Cg5 | 0.95 | 2.57 | 3.488 (5) | 163 |
C28—H28···Cg6iii | 0.95 | 2.65 | 3.557 (5) | 159 |
C123—H123···Cg7iv | 0.95 | 2.52 | 3.349 (5) | 146 |
C223—H223···Cg5iv | 0.95 | 2.53 | 3.359 (5) | 146 |
Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) −x+1/2, y−1/2, z−1/2; (iii) x+1/2, −y+3/2, z; (iv) x−1/2, −y+3/2, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C19H17NOS | C19H17NOS | C18H14BrNOS |
Mr | 307.41 | 307.41 | 372.27 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c | Orthorhombic, Pna21 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 7.0387 (3), 11.5605 (10), 18.1951 (17) | 16.165 (2), 5.2505 (3), 20.0410 (19) | 15.316 (2), 9.9230 (18), 20.225 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 118.813 (9), 90 | 90, 90, 90 |
V (Å3) | 1480.6 (2) | 1490.4 (3) | 3073.8 (8) |
Z | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.22 | 0.22 | 2.81 |
Crystal size (mm) | 0.34 × 0.24 × 0.14 | 0.41 × 0.23 × 0.12 | 0.40 × 0.14 × 0.12 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.929, 0.970 | 0.916, 0.974 | 0.399, 0.729 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13622, 2698, 1838 | 20766, 3412, 2058 | 27630, 6933, 5427 |
Rint | 0.129 | 0.082 | 0.049 |
(sin θ/λ)max (Å−1) | 0.606 | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.083, 0.99 | 0.057, 0.156, 1.08 | 0.038, 0.076, 1.03 |
No. of reflections | 2698 | 3412 | 6932 |
No. of parameters | 200 | 200 | 398 |
No. of restraints | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.62 | 0.35, −0.31 | 0.87, −0.43 |
Absolute structure | Flack (1983), 1333 Bijvoet pairs | ? | Flack (1983); this is not a conventional Flack x parameter but a twin
fraction, calculated using TWIN and BASF |
Absolute structure parameter | 0.03 (9) | ? | 0.663 (9) |
Selected geometrical parameters (Å, °) for compounds (I)–(III) top(i) Ring puckering parameters | | | | |
Parameter | (I) | (II) | (III) | |
| x = nul | x = nul | x = 1 | x = 2 |
(a) Five-membered rings | | | | |
Q2 | 0.447 (2) | 0.445 (3) | 0.466 (4) | 0.454 (4) |
ϕ2 | 16.0 (3) | 15.1 (4) | 21.3 (5) | 19.4 (5) |
| | | | |
(b) Six-membered rings | | | | |
Q | 0.615 (2) | 0.614 (3) | 0.626 (4) | 0.632 (4) |
θ | 128.8 (3) | 128.3 (3) | 127.1 (4) | 127.1 (4) |
ϕ | 162.2 (3) | 166.4 (4) | 162.2 (5) | 163.0 (5) |
| | | | |
(c) Seven-membered rings | | | | |
Q | 1.113 (3) | 1.112 (3) | 1.104 (4) | 1.107 (4) |
ϕ2 | 14.65 (16) | 16.61 (17) | 12.9 (2) | 13.6 (2) |
ϕ3 | 300.0 (5) | 299.7 (5) | 295.2 (7) | 297.9 (8) |
| | | | |
(ii) Torsion angles | | | | |
Mx1—Cx2—C2xx—Sxx21 | 31.0 (3) | -79.1 (3) | 33.6 (6) | 33.2 (5) |
Notes: puckering parameters for five-membered rings are defined for the
atom sequence Ox14–Nx1–Cx2–Cx3–Cx4,
puckering parameters for six-membered rings are defined for the atom sequence
Ox14–Nx1–Cx1B–Cx5A–Cx5–Cx4 and
puckering parameters for seven-membered rings are defined for the
atom sequence
Nx1–Cx2–Cx3–Cx4–Cx5–Cx5A–Cx1B. |
Parameters (Å, °) for hydrogen bonds in compounds (I)–(III) topCompound | D—H···A | | D—H | H···A | D···A | D—H···A |
(I) | C9—H9···O14i | | 0.95 | 2.51 | 3.425 (3) | 161 |
| C7—H7···Cg1ii | | 0.95 | 2.78 | 3.582 (3) | 143 |
| C24—H24···Cg2iii | | 0.95 | 2.64 | 3.572 (3) | 167 |
| C25—H25···Cg2iv | | 0.95 | 2.88 | 3.690 (3) | 143 |
| | | | | | |
(II) | C3—H3A···N1v | | 0.99 | 2.59 | 3.545 (4) | 163 |
| C5—H5B···O14v | | 0.99 | 2.50 | 3.436 (3) | 157 |
| | | | | | |
(III) | C14—H14···Cg3vi | | 1.00 | 2.75 | 3.616 (5) | 143 |
| C24—H24···Cg4vii | | 1.00 | 2.77 | 3.632 (5) | 145 |
| C18—H18···Cg5 | | 0.95 | 2.57 | 3.488 (5) | 163 |
| C28—H28···Cg6viii | | 0.95 | 2.65 | 3.557 (5) | 159 |
| C123—H123···Cg7ix | | 0.95 | 2.52 | 3.349 (5) | 146 |
| C223—H223···Cg5ix | | 0.95 | 2.53 | 3.359 (5) | 146 |
Cg1–7 represent the centroids of S21/C22–C25,
C7A/C8–C11/C11A, S221/C222–C225, S121/C122–C125,
C21A/C21B/C25A/C26/C27/C27A,
C17A/C18/C19/C110/C111/C11A and
C11A/C11B/C15A/C16/C17/C17A rings, respectively.
Symmetry codes:
(i) -x, y-1/2, -z+1/2;
(ii) -x+1/2, -y+1, z-1/2;
(iii) x+1/2, -y+1/2, -z+1;
(iv) -x+3/2, -y+1, z+1/2;
(v) x, y-1, z;
(vi) -x+1/2, y+1/2, z+1/2;
(vii) -x+1/2, y-1/2, z-1/2;
(viii) x+1/2, -y+3/2, z;
(ix) x-1/2, -y+3/2, z. |
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We have recently described a simple and efficient synthetic route to novel 2-aryl-substituted tetrahydro-1,4-epoxynaphtho[1,2-b]azepines (Palma et al., 2006), and the potential utility of this type of compounds as promising anti-Chagasic and leishmanicidal agents has also been demonstrated (Palma et al., 2009). In order to identify new antiparasitic compounds in the tetrahydronaphtho[1,2-b]azepine series, we have now achieved the synthesis of three thienyl-substituted analogues, namely (2R,4S)-2-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-b]azepine, (I), (2RS,4SR)-2-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-naphtho[1,2-b]azepine, (II), and (2RS,4SR)-2-(5-bromothiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-b]azepine, (III), whose molecular and supramolecular structures are reported here.
All three compounds (I)–(III) contain two stereogenic centres, at atoms C2 and C4 (Figs. 1–3). Compounds (II) and (III) both crystallize as racemic mixtures in the space groups P21/c and Pna21, with Z' = 1 and 2, respectively, but compound (I) crystallizes in the space group P212121, with just one enantiomer present in any individual crystal. In the crystal of (I) selected for data collection, the configuration is (2R,4S), and this configuration was selected for the reference molecules of compounds (II) and (III). The synthetic procedure provides no obvious scope for enantioselective discrimination and thus it seems likely that compound (I) is, in fact, formed in solution as a racemic mixture of (2R,4S) and (2S,4R) forms, but crystallizes as a conglomerate, rather that as a racemate, as found for compounds (II) and (III). The conditions under which racemic mixtures undergo spontaneous resolution via conglomerate crystallization have recently been much discussed (Lorenz et al., 2007; Gil-Hernández et al., 2010; Dupray, 2012; Gonnada et al., 2012; Pálovics et al., 2012).
For compounds (I)–(III), the conformations of the fused heterocyclic systems are similar, as shown (Table 1) by the ring-puckering parameters (Cremer & Pople, 1975) for the (2R,4S) forms. Similarly, the two independent molecules in compound (III) adopt very similar conformations. In every case, the five-membered ring is folded across the line Nx1···Cx4, while the six-membered rings all adopt conformations intermediate between the half-chair and envelope forms, for which the idealized values of the ring-puckering angles are θ = 129.2° and ϕ = (60k + 30)°, and θ = 125.3° and ϕ = 60k°, where k represents an integer. The conformational specification is completed by the torsion angle defining the orientation of the thienyl substituent with respect to the fused ring system (Table 2). These angles are similar in compounds (I) and (III), but that in (II) is rather different (cf. Figs. 1–3). However, there is no evidence for orientational disorder of any of the thienyl groups, such as is sometimes found for unsubstituted thienyl substituents (Trilleras et al., 2005, 2009; Cobo et al., 2006; Blanco et al., 2012).
Despite the similarities between compounds (I)–(III) in terms of their chemical constitution and their overall molecular shape, the intermolecular hydrogen bonds (Table 2) are different for all these compounds, as are the resultant supramolecular aggregation arrangements. Thus, for example, while the aggregation in (I) and (III) is dominated by C—H···π(arene) and C—H···π(thienyl) interactions, the structure of (I) also contains a C—H···O hydrogen bond, although such an interaction is absent from the structure of (III). On the other hand, the structure of compound (II) contains both C—H···N and C—H···O hydrogen bonds, but C—H···π interactions are absent. Although there is an unsubstituted aryl ring in each of (I)–(III), there are no aromatic π–π stacking interactions.
In compound (I), the combination of the C—H···O hydrogen bond and the two C—H···π(arene) hydrogen bonds (Table 2) suffices to generate a three-dimensional framework structure, which is modestly reinforced by the C—H···π(thienyl) interaction. The formation of the framework structure is readily analysed in terms of three independent one-dimensional sub-structures (Ferguson et al., 1998a,b; Gregson et al., 2000), each utilizing just one type of hydrogen bond. The C—H···O hydrogen bond links molecules related by the 21 screw axis along (0, y, 1/4) to form a C(8) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 4). The C—H···π(arene) hydrogen bonds having atoms C24 and C25 as the donors link molecules related, respectively, by the 21 screw axes along (1/4, 1/2, z) and (x, 1/4, 1/2) to generate chains running parallel to the [001] and [100] directions (Figs. 5 and 6). The combination of these three chains is then sufficient to link the molecules into a single three-dimensional framework.
Molecules of compound (II) related by translation along the [010] direction are linked by the C—H···N and C—H···O hydrogen bonds to form a C(4)C(4)[R22(7)] chain of rings (Fig. 7). There are no direction-specific interactions between the chains, so that the supramolecular assembly is just one-dimensional.
Compound (III) crystallizes with Z' = 2 (Fig. 3), however, it was possible to select an asymmetric unit in which the two molecules both had the (2R,4S) configuration and, in addition, were linked by a fairly short C—H···π(arene) hydrogen bond (Table 2). It will be convenient to refer to molecules containing atoms S121 or S221 as being of types 1 and 2, respectively. Three further C—H···π(arene) hydrogen bonds link molecules related by the a-glide plane at y = 0.75 into a chain of rings running parallel to the [100] direction (Fig. 8), while two C—H···π(thienyl) hydrogen bonds link molecules related by the n-glide plane at x = 0.25 into a second chain of rings, this time running parallel to the [011] direction (Fig. 9). The combination of [100] and [011] chains generates a complex sheet lying parallel to (011).
Although the ADDSYM routine in PLATON (Spek, 2009) showed that no additional crystallographic symmetry was present, despite the Z' value and the partial inversion twinning, there are, nonetheless, some close similarities between some of the corresponding pairs of hydrogen bonds. The two hydrogen bonds having atoms C14 and C24 as donors both link molecules of different types, so that a donor in a type 1 molecule combines with an acceptor in a type 2 molecule, and conversely; the acceptors are both thienyl units and their dimensions are very similar. Both generate chains along [011] and only the sense of the hydrogen bonds differs. The metrics of the two hydrogen bonds having atoms C123 and C223 as donors are also very similar, and they have corresponding aryl rings as the acceptors. Each of these interactions involves just a single type of molecule, type 1 or type 2 respectively, and the sense of the two hydrogen bonds is in the same direction along [100]. By contrast, the two hydrogen bonds having atoms C18 and C28 as donors use different types of aryl ring as the acceptors, namely the terminal aryl ring in the type 1 molecule and the internal aryl ring in the type 2 molecule (Table 2, Fig. 3); unsurprisingly, therefore, the dimensions for these two hydrogen bonds differ somewhat. In the type 1 molecule, both rings of the naphthalene unit act as single acceptors, with donors on opposite faces of this unit, whereas in the type 2 molecule, the internal aryl rings acts as a double acceptor, again with the two donors on opposite faces of the ring such that H18···Cg5···H223i = 172° [Cg5 represents the centroid of the C21A/C21B/C25A/C26/C27/C27A ring; symmetry code: (i) x+1/2, -y+3/2, z]. This contrast is sufficient to preclude the possibility of any additional crystallographic symmetry.
It is of interest briefly to compare the supramolecular assembly in compounds (I)–(III) reported here with that in compounds (IV)–(VI) (Palma et al., 2009) and (VII) (Yépes et al., 2012) (see Scheme). The molecules of compound (IV), which exhibits partial inversion twinning in the space group P21, are linked into sheets by a combination of one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds, while those of compound (VI) are linked into a three-dimensional array by one C—H···O and four C—H···π(arene) hydrogen bonds. The isomeric compounds (V) and (VII) crystallize in different space groups, viz. Pbca and P21/c, respectively; in (V), the molecules are linked by a single C—H···O hydrogen bond to form chains which are themselves linked into sheets by an aromatic π–π stacking interaction, while in (VII), chains formed by C—H···π(arene) hydrogen bonds are again π-stacked to form sheets. It may be recalled here that aromatic π–π stacking interactions are absent from the structures of (I)–(III). Thus, the seven closely related compounds (I)–(VII), as well as crystallizing in five different space groups, all show different patterns of direction-specific intermolecular interactions with corresponding differences in the overall supramolecular assembly.