Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802000958/cv6083sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802000958/cv6083Isup2.hkl |
CCDC reference: 182593
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.003 Å
- R factor = 0.052
- wR factor = 0.138
- Data-to-parameter ratio = 18.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
To a stirred solution of bridged diester (75 g, 0.14 mol), prepared from the Pummerer reaction of a keto-sulfoxide (Sarkar et al., 2002) in dry toluene (12 ml), was added 1,8-iazabicyclo[5,4.0]undec-7-ene (0.21 ml, 1.45 mol). The mixture was refluxed for 1.5 h. After cooling to room temperature, water was added to the mixture. The aqueous layer was separated and extracted with ether, dried with Na2SO4, and concentrated in vacuo. The residue was purified by column chromatography on silica gel, and finally recrystallized from an ethyl acetate-petroleum ether solution to give yellow single crystals.
After checking their presence in a difference map, all the H atoms were placed at geometrically calculated positions and were refined as riding-model atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C25H17Cl2NO4S | Dx = 1.472 Mg m−3 |
Mr = 498.36 | Melting point: 451-452 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8487 (1) Å | Cell parameters from 6457 reflections |
b = 12.6944 (1) Å | θ = 2.6–28.3° |
c = 32.6567 (3) Å | µ = 0.42 mm−1 |
V = 4497.4 (1) Å3 | T = 183 K |
Z = 8 | Slab, yellow |
F(000) = 2048 | 0.40 × 0.32 × 0.12 mm |
Siemens SMART CCD area-detector diffractometer | 5513 independent reflections |
Radiation source: fine-focus sealed tube | 3836 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.6° |
ω scans | h = −14→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −16→10 |
Tmin = 0.851, Tmax = 0.952 | l = −39→43 |
25577 measured reflections |
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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0709P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
5513 reflections | Δρmax = 0.46 e Å−3 |
301 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0052 (6) |
C25H17Cl2NO4S | V = 4497.4 (1) Å3 |
Mr = 498.36 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.8487 (1) Å | µ = 0.42 mm−1 |
b = 12.6944 (1) Å | T = 183 K |
c = 32.6567 (3) Å | 0.40 × 0.32 × 0.12 mm |
Siemens SMART CCD area-detector diffractometer | 5513 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3836 reflections with I > 2σ(I) |
Tmin = 0.851, Tmax = 0.952 | Rint = 0.093 |
25577 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.46 e Å−3 |
5513 reflections | Δρmin = −0.41 e Å−3 |
301 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 | ||
S1 | 0.25989 (5) | 0.66546 (5) | 0.105916 (18) | 0.02257 (16) | |
Cl1 | −0.07308 (8) | 0.23165 (6) | 0.04895 (2) | 0.0452 (2) | |
Cl2 | 0.20583 (6) | 0.45899 (6) | −0.039946 (18) | 0.03696 (19) | |
O1 | 0.07394 (15) | 0.64709 (14) | 0.20668 (5) | 0.0324 (4) | |
O2 | 0.26755 (15) | 0.58816 (14) | 0.19865 (5) | 0.0269 (4) | |
O3 | −0.12207 (15) | 0.43194 (15) | 0.20996 (5) | 0.0313 (4) | |
O4 | 0.07793 (15) | 0.40436 (13) | 0.22478 (5) | 0.0260 (4) | |
N1 | 0.07058 (19) | 0.35817 (17) | 0.01297 (6) | 0.0258 (5) | |
C1 | 0.04441 (19) | 0.40293 (17) | 0.08513 (7) | 0.0173 (5) | |
C2 | 0.0226 (2) | 0.34076 (18) | 0.04884 (7) | 0.0230 (5) | |
C3 | 0.1462 (2) | 0.4410 (2) | 0.00896 (7) | 0.0246 (5) | |
C4 | 0.1771 (2) | 0.50744 (19) | 0.03971 (7) | 0.0228 (5) | |
H4 | 0.2303 | 0.5636 | 0.0351 | 0.027* | |
C5 | 0.12649 (19) | 0.48959 (17) | 0.07909 (7) | 0.0172 (5) | |
C6 | 0.15881 (19) | 0.55593 (17) | 0.11310 (7) | 0.0169 (4) | |
C7 | 0.11659 (19) | 0.53105 (17) | 0.15154 (6) | 0.0163 (4) | |
C8 | 0.03230 (19) | 0.44653 (17) | 0.15714 (6) | 0.0164 (4) | |
C9 | −0.00699 (19) | 0.38438 (17) | 0.12492 (6) | 0.0162 (4) | |
C10 | −0.10114 (19) | 0.30140 (17) | 0.13418 (6) | 0.0170 (4) | |
C11 | −0.2251 (2) | 0.3207 (2) | 0.12660 (8) | 0.0305 (6) | |
H11 | −0.2493 | 0.3844 | 0.1151 | 0.037* | |
C12 | −0.3123 (2) | 0.2457 (2) | 0.13612 (9) | 0.0353 (7) | |
H12 | −0.3952 | 0.2595 | 0.1314 | 0.042* | |
C13 | −0.2775 (2) | 0.1510 (2) | 0.15255 (8) | 0.0316 (6) | |
H13 | −0.3363 | 0.0994 | 0.1578 | 0.038* | |
C14 | −0.1560 (2) | 0.1323 (2) | 0.16122 (8) | 0.0310 (6) | |
H14 | −0.1328 | 0.0689 | 0.1732 | 0.037* | |
C15 | −0.0677 (2) | 0.20730 (18) | 0.15218 (7) | 0.0224 (5) | |
H15 | 0.0147 | 0.1943 | 0.1583 | 0.027* | |
C16 | 0.1544 (2) | 0.77203 (17) | 0.09981 (7) | 0.0193 (5) | |
C17 | 0.0859 (2) | 0.7843 (2) | 0.06419 (8) | 0.0302 (6) | |
H17 | 0.0888 | 0.7333 | 0.0438 | 0.036* | |
C18 | 0.0131 (3) | 0.8735 (2) | 0.05930 (8) | 0.0372 (7) | |
H18 | −0.0326 | 0.8823 | 0.0354 | 0.045* | |
C19 | 0.0081 (2) | 0.9494 (2) | 0.08964 (9) | 0.0339 (6) | |
H19 | −0.0402 | 1.0092 | 0.0861 | 0.041* | |
C20 | 0.0742 (2) | 0.9362 (2) | 0.12486 (8) | 0.0282 (6) | |
H20 | 0.0701 | 0.9872 | 0.1453 | 0.034* | |
C21 | 0.1473 (2) | 0.84774 (19) | 0.13057 (7) | 0.0241 (5) | |
H21 | 0.1912 | 0.8391 | 0.1548 | 0.029* | |
C22 | −0.0166 (2) | 0.42686 (17) | 0.19974 (7) | 0.0208 (5) | |
C23 | 0.0460 (3) | 0.3898 (2) | 0.26773 (7) | 0.0391 (7) | |
H23A | 0.1200 | 0.3827 | 0.2836 | 0.059* | |
H23B | −0.0032 | 0.3274 | 0.2707 | 0.059* | |
H23C | 0.0002 | 0.4497 | 0.2772 | 0.059* | |
C24 | 0.1489 (2) | 0.59632 (17) | 0.18847 (7) | 0.0204 (5) | |
C25 | 0.3041 (3) | 0.6502 (2) | 0.23393 (8) | 0.0388 (7) | |
H25A | 0.3909 | 0.6417 | 0.2386 | 0.058* | |
H25B | 0.2594 | 0.6268 | 0.2576 | 0.058* | |
H25C | 0.2862 | 0.7231 | 0.2289 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0181 (3) | 0.0151 (3) | 0.0346 (3) | −0.0031 (2) | −0.0003 (2) | 0.0037 (3) |
Cl1 | 0.0735 (5) | 0.0363 (4) | 0.0260 (3) | −0.0305 (4) | 0.0003 (3) | −0.0059 (3) |
Cl2 | 0.0466 (4) | 0.0403 (4) | 0.0240 (3) | 0.0075 (3) | 0.0116 (3) | 0.0048 (3) |
O1 | 0.0322 (10) | 0.0284 (10) | 0.0367 (10) | 0.0036 (8) | 0.0032 (8) | −0.0138 (9) |
O2 | 0.0240 (9) | 0.0295 (10) | 0.0273 (9) | −0.0012 (7) | −0.0055 (7) | −0.0060 (8) |
O3 | 0.0265 (9) | 0.0354 (11) | 0.0320 (9) | −0.0034 (8) | 0.0108 (7) | −0.0060 (8) |
O4 | 0.0336 (9) | 0.0245 (9) | 0.0199 (8) | 0.0008 (7) | −0.0016 (7) | 0.0043 (7) |
N1 | 0.0324 (11) | 0.0252 (11) | 0.0197 (10) | 0.0020 (9) | −0.0034 (8) | −0.0009 (9) |
C1 | 0.0185 (10) | 0.0134 (11) | 0.0201 (11) | 0.0010 (9) | −0.0020 (8) | 0.0032 (9) |
C2 | 0.0265 (12) | 0.0154 (11) | 0.0272 (12) | −0.0033 (10) | −0.0052 (9) | 0.0022 (10) |
C3 | 0.0290 (13) | 0.0249 (13) | 0.0199 (11) | 0.0069 (10) | 0.0037 (9) | 0.0050 (10) |
C4 | 0.0217 (11) | 0.0203 (12) | 0.0264 (12) | 0.0026 (9) | 0.0050 (9) | 0.0051 (10) |
C5 | 0.0163 (10) | 0.0125 (10) | 0.0230 (11) | 0.0019 (8) | −0.0009 (8) | 0.0019 (9) |
C6 | 0.0138 (10) | 0.0113 (10) | 0.0256 (11) | 0.0009 (8) | −0.0008 (8) | 0.0010 (9) |
C7 | 0.0151 (10) | 0.0118 (10) | 0.0219 (11) | 0.0020 (8) | −0.0007 (8) | −0.0007 (9) |
C8 | 0.0161 (10) | 0.0131 (11) | 0.0201 (10) | 0.0007 (8) | 0.0001 (8) | 0.0017 (9) |
C9 | 0.0151 (10) | 0.0117 (10) | 0.0217 (11) | 0.0004 (8) | −0.0014 (8) | 0.0025 (9) |
C10 | 0.0189 (10) | 0.0137 (11) | 0.0184 (10) | −0.0026 (9) | 0.0010 (8) | −0.0002 (9) |
C11 | 0.0237 (12) | 0.0213 (13) | 0.0465 (16) | −0.0020 (10) | −0.0057 (11) | 0.0074 (12) |
C12 | 0.0202 (12) | 0.0351 (16) | 0.0506 (17) | −0.0057 (11) | −0.0045 (11) | 0.0075 (14) |
C13 | 0.0297 (13) | 0.0275 (14) | 0.0375 (15) | −0.0159 (11) | 0.0049 (11) | 0.0043 (12) |
C14 | 0.0373 (14) | 0.0176 (12) | 0.0381 (14) | 0.0005 (11) | 0.0069 (11) | 0.0111 (11) |
C15 | 0.0186 (11) | 0.0191 (12) | 0.0293 (12) | 0.0022 (9) | 0.0019 (9) | 0.0049 (10) |
C16 | 0.0207 (11) | 0.0114 (11) | 0.0258 (12) | −0.0044 (9) | 0.0004 (9) | 0.0023 (9) |
C17 | 0.0429 (15) | 0.0227 (13) | 0.0250 (12) | 0.0069 (11) | −0.0050 (11) | −0.0032 (11) |
C18 | 0.0448 (16) | 0.0362 (16) | 0.0306 (14) | 0.0121 (13) | −0.0101 (12) | 0.0031 (13) |
C19 | 0.0307 (14) | 0.0185 (13) | 0.0524 (17) | 0.0056 (11) | 0.0007 (12) | 0.0062 (13) |
C20 | 0.0312 (13) | 0.0160 (12) | 0.0373 (14) | −0.0038 (10) | 0.0051 (11) | −0.0067 (11) |
C21 | 0.0256 (12) | 0.0200 (12) | 0.0266 (12) | −0.0051 (10) | −0.0014 (9) | −0.0011 (10) |
C22 | 0.0269 (12) | 0.0103 (11) | 0.0253 (12) | −0.0021 (9) | 0.0016 (9) | −0.0025 (9) |
C23 | 0.065 (2) | 0.0324 (16) | 0.0203 (13) | −0.0022 (14) | 0.0025 (12) | 0.0061 (12) |
C24 | 0.0256 (12) | 0.0126 (11) | 0.0231 (11) | −0.0024 (9) | 0.0005 (9) | 0.0013 (9) |
C25 | 0.0462 (16) | 0.0390 (17) | 0.0312 (14) | −0.0123 (14) | −0.0136 (12) | −0.0059 (13) |
S1—C16 | 1.783 (2) | C11—C12 | 1.377 (3) |
S1—C6 | 1.786 (2) | C11—H11 | 0.9300 |
Cl1—C2 | 1.731 (2) | C12—C13 | 1.370 (4) |
Cl2—C3 | 1.738 (2) | C12—H12 | 0.9300 |
O1—C24 | 1.196 (3) | C13—C14 | 1.368 (4) |
O2—C24 | 1.334 (3) | C13—H13 | 0.9300 |
O2—C25 | 1.451 (3) | C14—C15 | 1.383 (3) |
O3—C22 | 1.194 (3) | C14—H14 | 0.9300 |
O4—C22 | 1.342 (3) | C15—H15 | 0.9300 |
O4—C23 | 1.456 (3) | C16—C17 | 1.389 (3) |
N1—C2 | 1.301 (3) | C16—C21 | 1.392 (3) |
N1—C3 | 1.340 (3) | C17—C18 | 1.390 (4) |
C1—C5 | 1.429 (3) | C17—H17 | 0.9300 |
C1—C9 | 1.433 (3) | C18—C19 | 1.383 (4) |
C1—C2 | 1.443 (3) | C18—H18 | 0.9300 |
C3—C4 | 1.353 (3) | C19—C20 | 1.365 (4) |
C4—C5 | 1.416 (3) | C19—H19 | 0.9300 |
C4—H4 | 0.9300 | C20—C21 | 1.387 (3) |
C5—C6 | 1.437 (3) | C20—H20 | 0.9300 |
C6—C7 | 1.373 (3) | C21—H21 | 0.9300 |
C7—C8 | 1.422 (3) | C23—H23A | 0.9600 |
C7—C24 | 1.505 (3) | C23—H23B | 0.9600 |
C8—C9 | 1.383 (3) | C23—H23C | 0.9600 |
C8—C22 | 1.510 (3) | C25—H25A | 0.9600 |
C9—C10 | 1.498 (3) | C25—H25B | 0.9600 |
C10—C15 | 1.380 (3) | C25—H25C | 0.9600 |
C10—C11 | 1.389 (3) | ||
C16—S1—C6 | 102.19 (10) | C13—C14—C15 | 120.3 (2) |
C24—O2—C25 | 114.82 (19) | C13—C14—H14 | 119.9 |
C22—O4—C23 | 115.6 (2) | C15—C14—H14 | 119.9 |
C2—N1—C3 | 117.8 (2) | C10—C15—C14 | 120.3 (2) |
C5—C1—C9 | 119.6 (2) | C10—C15—H15 | 119.9 |
C5—C1—C2 | 114.20 (19) | C14—C15—H15 | 119.9 |
C9—C1—C2 | 126.2 (2) | C17—C16—C21 | 119.8 (2) |
N1—C2—C1 | 125.5 (2) | C17—C16—S1 | 121.47 (18) |
N1—C2—Cl1 | 112.20 (18) | C21—C16—S1 | 118.59 (17) |
C1—C2—Cl1 | 122.31 (17) | C16—C17—C18 | 119.4 (2) |
N1—C3—C4 | 124.6 (2) | C16—C17—H17 | 120.3 |
N1—C3—Cl2 | 114.88 (18) | C18—C17—H17 | 120.3 |
C4—C3—Cl2 | 120.52 (19) | C19—C18—C17 | 120.5 (2) |
C3—C4—C5 | 118.6 (2) | C19—C18—H18 | 119.8 |
C3—C4—H4 | 120.7 | C17—C18—H18 | 119.8 |
C5—C4—H4 | 120.7 | C20—C19—C18 | 119.9 (2) |
C4—C5—C1 | 119.3 (2) | C20—C19—H19 | 120.1 |
C4—C5—C6 | 120.9 (2) | C18—C19—H19 | 120.1 |
C1—C5—C6 | 119.76 (19) | C19—C20—C21 | 120.8 (2) |
C7—C6—C5 | 119.36 (19) | C19—C20—H20 | 119.6 |
C7—C6—S1 | 120.26 (17) | C21—C20—H20 | 119.6 |
C5—C6—S1 | 120.29 (16) | C20—C21—C16 | 119.6 (2) |
C6—C7—C8 | 120.39 (19) | C20—C21—H21 | 120.2 |
C6—C7—C24 | 121.90 (19) | C16—C21—H21 | 120.2 |
C8—C7—C24 | 117.53 (18) | O3—C22—O4 | 125.0 (2) |
C9—C8—C7 | 122.08 (19) | O3—C22—C8 | 125.8 (2) |
C9—C8—C22 | 119.91 (19) | O4—C22—C8 | 109.17 (18) |
C7—C8—C22 | 118.00 (19) | O4—C23—H23A | 109.5 |
C8—C9—C1 | 118.43 (19) | O4—C23—H23B | 109.5 |
C8—C9—C10 | 117.25 (19) | H23A—C23—H23B | 109.5 |
C1—C9—C10 | 124.32 (19) | O4—C23—H23C | 109.5 |
C15—C10—C11 | 118.9 (2) | H23A—C23—H23C | 109.5 |
C15—C10—C9 | 121.01 (19) | H23B—C23—H23C | 109.5 |
C11—C10—C9 | 120.0 (2) | O1—C24—O2 | 125.0 (2) |
C12—C11—C10 | 120.2 (2) | O1—C24—C7 | 122.5 (2) |
C12—C11—H11 | 119.9 | O2—C24—C7 | 112.46 (18) |
C10—C11—H11 | 119.9 | O2—C25—H25A | 109.5 |
C13—C12—C11 | 120.4 (2) | O2—C25—H25B | 109.5 |
C13—C12—H12 | 119.8 | H25A—C25—H25B | 109.5 |
C11—C12—H12 | 119.8 | O2—C25—H25C | 109.5 |
C14—C13—C12 | 119.9 (2) | H25A—C25—H25C | 109.5 |
C14—C13—H13 | 120.1 | H25B—C25—H25C | 109.5 |
C12—C13—H13 | 120.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23B···O1i | 0.96 | 2.52 | 3.447 (3) | 161 |
C12—H12···Cg(A)ii | 0.93 | 2.67 | 3.524 (3) | 153 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x−3/2, y−3/2, z. |
Experimental details
Crystal data | |
Chemical formula | C25H17Cl2NO4S |
Mr | 498.36 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 183 |
a, b, c (Å) | 10.8487 (1), 12.6944 (1), 32.6567 (3) |
V (Å3) | 4497.4 (1) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.40 × 0.32 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.851, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25577, 5513, 3836 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.138, 0.97 |
No. of reflections | 5513 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.41 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23B···O1i | 0.96 | 2.52 | 3.447 (3) | 161 |
C12—H12···Cg(A)ii | 0.93 | 2.67 | 3.524 (3) | 153 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x−3/2, y−3/2, z. |
Lignans, which are characterized by the presence of two phenylpropane moieties bonded through C8—C8', as in (I) in the Scheme below, have generated much interest in view of their widespread occurance in the nature and their biological activities (Ward, 1993). In recent years, a class of compounds having the lignan skeleton with one or two heteroatoms in the phenylpropane units has been developed in various research laboratories (Ramos et al., 1999). This class of compounds, i.e. heterolignans, are of wide structural diversity and possess not only biological activities comparable to lignans but also display either enhanced biological activities or variety of other properties. In view of the importance of these heterolignans, we have conducted a synthesis program in order to investigate the structure–activity relationship of lignans (II) and (III). During the course of this work, we have synthesized the substituted isoquinoline (IV) which is related to the heterolignans (II) and (III). An X-ray structure determination of (IV) was undertaken in order to elucidate the molecular conformation.
In the structure of (IV) (Fig. 1), the bond lengths and angles are normal (Allen et al., 1987). Atoms Cl1 and Cl2 lie on the isoquinoline (C1–C9/N1) plane, with displacements of 0.031 (1) and 0.050 (1) Å, respectively. Both of the attached methyl carboxylates (O1/O2/C24/C25 and O3/O4/C22/C25) form planes, and the two planes are twisted out of the isoquinoline by 64.8 (1) and 63.0 (1)°, respectively.
The C10–C15 phenyl ring attached to atom C9 is nearly perpendicular to the isoquinoline plane, with a twisted angle of 82.7 (1)°, The C6—S1—C16 angle joining the C16–C21 phenyl ring to the isoquinoline system is 102.2 (1)°, while the dihedral angle between this phenyl ring and the isoquinoline is 76.6 (1)°.
In the crystal packing structure of (IV), the molecules are linked by C23—H23B···O1i hydrogen bonds (Table 1) to form an infinite chain along the b direction (Fig. 2). The molecular chains form sheets perpendicular to the a direction. An intermolecular C—H···π interaction is observed involving the centroid of the phenyl C16–C21 ring. In Table 1, the center of gravity of the phenyl ring is denoted Cg(A).