The title compounds, C22H18Cl2N2O4S, (I), and C22H19ClN2O4S, (II), respectively, are structural cyclic imide analogues of pharmaceutical interest. The configurations exo-endo for (I) and endo-endo for (II) were established.
Supporting information
CCDC references: 248180; 248181
For the preparation of the exo-endo compound, (I), p-toluenesulfonylazide (2.00 g, 10.1 mmol) was added to a mixture of 4-(3',4'-dichlorophenyl)-4-azatricycle[5.2.1.02,6-endo]dec-8-ene-3,5-dione (2.50 g, 8.11 mmol) in acetonitrile (25 ml), prepared as described by Salakhov et al. (1979) and Chenier et al. (1992). The reaction was refluxed for 18 h and the solvent was evaporated in vacuo. The solid residue was triturated with methanol-chloroform (3:7) and filtered off with suction to give the crude product. The formation of the endo-endo isomer was also observed together with (I), but unfortunately the endo-endo isomer could not afford crystals for X-ray studies. The exo-endo and endo-endo isomers were isolated by column chromatography (silica gel, dichloromethane-hexane, 1:4). For the preparation of the endo-endo compound, (II), p-toluenesulfonylazide (2.92 g, 14.8 mmol) was added to 4-(4'-chlorophenyl)-4-azatricycle[5.2.1.02,6-endo]dec-8-ene-3,5-dione (2.00 g, 7.31 mmol) in acetonitrile (20 ml), prepared as described by Salakhov et al. (1979) and Chenier et al. (1992). The reaction was refluxed for 18 h and the solvent was evaporated in vacuo. The solid residue was triturated with methanol-chloroform (3:7) and filtered off with suction to give the crude product. The endo-endo and exo-endo products were purified by column chromatography (silica gel, ethyl acetate-acetone-hexane, 6:3:11). The exo-endo isomer could not afford crystals for X-ray analysis. Compounds (I) and (II) were crystallized from solutions in methanol-chloroform (1:2) by slow evaporation of the solvent mixture.
H atoms were placed in idealized positions and refined using a riding model, with C—H distances of 0.98, 0.97, 0.96 and 0.93 Å, and with Uiso(H) fixed at 1.2, 1.2, 1.5 and 1.2Ueq(C), for CH, CH2, CH3 and CHarom, respectively. In (I), a C2 rotation on the N6—C12 bond causes structural disorder at atom Cl2, which is partially bonded to atoms C14 and C16, with occupancy factors of 0.862 (3) and 0.138 (3), respectively. The complementary occupancy factors at atoms C14 and C16 are occupied by H atoms fixed geometrically. The H atoms on C27 were placed in the atom list using an idealized disordered model for a methyl group.
For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: SET4 in CAD-4 EXPRESS; data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrgia, 1997); software used to prepare material for publication: SHELXL97.
(I) 4-(3,4-Dichlorophenyl)-9-(4-methylphenylsulfonyl)-4,9- diazatetracyclo[5.3.1.0
2,6.0
8,10]undecane-3,5-dione
top
Crystal data top
C22H18Cl2N2O4S | F(000) = 984 |
Mr = 477.34 | Dx = 1.489 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 12.856 (1) Å | θ = 6.6–12.2° |
b = 15.689 (1) Å | µ = 0.44 mm−1 |
c = 10.727 (1) Å | T = 293 K |
β = 100.27 (1)° | Irregular plate, colourless |
V = 2128.9 (3) Å3 | 0.50 × 0.40 × 0.10 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2300 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 25.1°, θmin = 1.6° |
ω/2θ scans | h = −15→0 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.844, Tmax = 0.934 | l = −12→12 |
3962 measured reflections | 3 standard reflections every 200 reflections |
3785 independent reflections | intensity decay: 1% |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0571P)2 + 1.0126P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3785 reflections | Δρmax = 0.52 e Å−3 |
291 parameters | Δρmin = −0.46 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0073 (9) |
Crystal data top
C22H18Cl2N2O4S | V = 2128.9 (3) Å3 |
Mr = 477.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.856 (1) Å | µ = 0.44 mm−1 |
b = 15.689 (1) Å | T = 293 K |
c = 10.727 (1) Å | 0.50 × 0.40 × 0.10 mm |
β = 100.27 (1)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2300 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.028 |
Tmin = 0.844, Tmax = 0.934 | 3 standard reflections every 200 reflections |
3962 measured reflections | intensity decay: 1% |
3785 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.52 e Å−3 |
3785 reflections | Δρmin = −0.46 e Å−3 |
291 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.34269 (8) | 0.08587 (5) | 0.30464 (8) | 0.0425 (3) | |
O1 | 0.2869 (2) | 0.06278 (16) | 0.1819 (2) | 0.0653 (8) | |
O2 | 0.4527 (2) | 0.06481 (15) | 0.3339 (3) | 0.0573 (7) | |
Cl1 | 1.07173 (11) | 0.26492 (11) | 0.57310 (18) | 0.1251 (7) | |
Cl2 | 1.00000 (12) | 0.41038 (13) | 0.3801 (2) | 0.1323 (10) | 0.863 (3) |
Cl2' | 0.9165 (7) | 0.1692 (7) | 0.6638 (9) | 0.091 (4) | 0.137 (3) |
N1 | 0.3210 (2) | 0.18931 (16) | 0.3190 (2) | 0.0358 (6) | |
C2 | 0.4030 (2) | 0.24479 (19) | 0.2774 (3) | 0.0334 (7) | |
H2 | 0.4616 | 0.2200 | 0.2424 | 0.040* | |
C3 | 0.3635 (2) | 0.3348 (2) | 0.2418 (3) | 0.0370 (8) | |
H3 | 0.3387 | 0.3452 | 0.1513 | 0.044* | |
C4 | 0.4536 (3) | 0.3936 (2) | 0.3076 (3) | 0.0381 (8) | |
H4 | 0.4418 | 0.4524 | 0.2774 | 0.046* | |
C5 | 0.5643 (3) | 0.3653 (2) | 0.3002 (3) | 0.0395 (8) | |
O3 | 0.60126 (19) | 0.35337 (16) | 0.2056 (2) | 0.0525 (7) | |
N6 | 0.6188 (2) | 0.35146 (17) | 0.4237 (3) | 0.0407 (7) | |
C7 | 0.5551 (3) | 0.3626 (2) | 0.5158 (3) | 0.0410 (8) | |
O4 | 0.58547 (19) | 0.35425 (18) | 0.6279 (2) | 0.0586 (7) | |
C8 | 0.4457 (2) | 0.3874 (2) | 0.4496 (3) | 0.0378 (8) | |
H8 | 0.4258 | 0.4427 | 0.4807 | 0.045* | |
C9 | 0.3554 (2) | 0.3217 (2) | 0.4504 (3) | 0.0351 (8) | |
H9 | 0.3238 | 0.3211 | 0.5271 | 0.042* | |
C10 | 0.3985 (2) | 0.23697 (19) | 0.4139 (3) | 0.0309 (7) | |
H10 | 0.4541 | 0.2070 | 0.4719 | 0.037* | |
C11 | 0.2818 (3) | 0.3494 (2) | 0.3285 (3) | 0.0418 (8) | |
H11A | 0.2602 | 0.4086 | 0.3307 | 0.050* | |
H11B | 0.2203 | 0.3129 | 0.3073 | 0.050* | |
C12 | 0.7279 (3) | 0.3275 (2) | 0.4551 (3) | 0.0425 (8) | |
C13 | 0.8017 (3) | 0.3743 (3) | 0.4081 (4) | 0.0569 (11) | |
H13 | 0.7809 | 0.4198 | 0.3539 | 0.068* | |
C14 | 0.9079 (3) | 0.3535 (3) | 0.4416 (5) | 0.0724 (13) | |
H14 | 0.9582 | 0.3841 | 0.4077 | 0.087* | 0.137 (3) |
C15 | 0.9389 (3) | 0.2878 (3) | 0.5243 (5) | 0.0669 (12) | |
C16 | 0.8644 (4) | 0.2408 (3) | 0.5700 (4) | 0.0649 (12) | |
H16 | 0.8851 | 0.1955 | 0.6248 | 0.078* | 0.863 (3) |
C17 | 0.7583 (3) | 0.2600 (2) | 0.5349 (4) | 0.0538 (10) | |
H17 | 0.7078 | 0.2274 | 0.5652 | 0.065* | |
C21 | 0.2794 (3) | 0.0440 (2) | 0.4239 (3) | 0.0389 (8) | |
C22 | 0.3314 (3) | −0.0179 (2) | 0.5025 (3) | 0.0442 (9) | |
H22 | 0.3990 | −0.0353 | 0.4940 | 0.053* | |
C23 | 0.2821 (3) | −0.0537 (2) | 0.5937 (3) | 0.0500 (9) | |
H23 | 0.3167 | −0.0962 | 0.6457 | 0.060* | |
C24 | 0.1832 (3) | −0.0282 (2) | 0.6098 (3) | 0.0488 (9) | |
C25 | 0.1338 (3) | 0.0360 (3) | 0.5322 (4) | 0.0579 (10) | |
H25 | 0.0679 | 0.0556 | 0.5438 | 0.069* | |
C26 | 0.1807 (3) | 0.0715 (2) | 0.4381 (4) | 0.0507 (10) | |
H26 | 0.1459 | 0.1134 | 0.3852 | 0.061* | |
C27 | 0.1304 (4) | −0.0691 (3) | 0.7100 (4) | 0.0753 (13) | |
H27A | 0.0621 | −0.0438 | 0.7080 | 0.113* | 0.50 |
H27B | 0.1732 | −0.0604 | 0.7919 | 0.113* | 0.50 |
H27C | 0.1224 | −0.1292 | 0.6936 | 0.113* | 0.50 |
H27D | 0.1763 | −0.1117 | 0.7544 | 0.113* | 0.50 |
H27E | 0.0653 | −0.0952 | 0.6705 | 0.113* | 0.50 |
H27F | 0.1161 | −0.0264 | 0.7688 | 0.113* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0591 (6) | 0.0301 (4) | 0.0411 (5) | −0.0069 (4) | 0.0162 (4) | −0.0032 (4) |
O1 | 0.112 (2) | 0.0470 (15) | 0.0371 (14) | −0.0260 (15) | 0.0131 (15) | −0.0077 (12) |
O2 | 0.0585 (16) | 0.0403 (14) | 0.082 (2) | 0.0076 (12) | 0.0352 (14) | 0.0070 (13) |
Cl1 | 0.0539 (8) | 0.1333 (14) | 0.1814 (17) | 0.0327 (8) | 0.0032 (9) | 0.0173 (12) |
Cl2 | 0.0524 (9) | 0.1227 (15) | 0.233 (2) | −0.0053 (9) | 0.0550 (12) | 0.0662 (15) |
Cl2' | 0.084 (7) | 0.111 (8) | 0.078 (6) | 0.039 (6) | 0.017 (5) | 0.038 (5) |
N1 | 0.0406 (15) | 0.0310 (14) | 0.0358 (16) | −0.0053 (12) | 0.0066 (12) | 0.0008 (12) |
C2 | 0.0355 (18) | 0.0326 (17) | 0.0318 (17) | −0.0039 (14) | 0.0050 (14) | −0.0018 (14) |
C3 | 0.0433 (19) | 0.0376 (18) | 0.0297 (17) | 0.0013 (15) | 0.0050 (15) | 0.0047 (14) |
C4 | 0.045 (2) | 0.0261 (17) | 0.044 (2) | 0.0009 (14) | 0.0111 (16) | 0.0042 (14) |
C5 | 0.045 (2) | 0.0305 (18) | 0.046 (2) | −0.0068 (15) | 0.0156 (17) | 0.0040 (16) |
O3 | 0.0599 (16) | 0.0561 (16) | 0.0479 (15) | −0.0016 (13) | 0.0268 (13) | 0.0039 (12) |
N6 | 0.0384 (16) | 0.0393 (16) | 0.0472 (18) | −0.0050 (13) | 0.0146 (14) | 0.0021 (13) |
C7 | 0.045 (2) | 0.0362 (19) | 0.044 (2) | −0.0089 (16) | 0.0147 (17) | −0.0084 (16) |
O4 | 0.0505 (15) | 0.087 (2) | 0.0383 (15) | −0.0037 (14) | 0.0074 (12) | −0.0110 (14) |
C8 | 0.0420 (19) | 0.0313 (17) | 0.0416 (19) | −0.0020 (15) | 0.0116 (16) | −0.0074 (14) |
C9 | 0.0370 (18) | 0.0368 (18) | 0.0344 (18) | −0.0007 (15) | 0.0138 (15) | −0.0049 (15) |
C10 | 0.0329 (17) | 0.0306 (17) | 0.0287 (17) | −0.0038 (14) | 0.0044 (14) | 0.0004 (13) |
C11 | 0.0396 (19) | 0.0352 (19) | 0.050 (2) | 0.0033 (15) | 0.0053 (16) | 0.0020 (16) |
C12 | 0.0377 (19) | 0.039 (2) | 0.052 (2) | −0.0008 (16) | 0.0109 (17) | −0.0039 (17) |
C13 | 0.039 (2) | 0.049 (2) | 0.085 (3) | 0.0022 (18) | 0.020 (2) | 0.014 (2) |
C14 | 0.045 (2) | 0.062 (3) | 0.115 (4) | −0.005 (2) | 0.025 (2) | 0.009 (3) |
C15 | 0.046 (2) | 0.061 (3) | 0.092 (3) | 0.013 (2) | 0.009 (2) | −0.003 (3) |
C16 | 0.068 (3) | 0.058 (3) | 0.068 (3) | 0.022 (2) | 0.012 (2) | 0.009 (2) |
C17 | 0.056 (2) | 0.042 (2) | 0.064 (3) | 0.0012 (19) | 0.013 (2) | 0.0047 (19) |
C21 | 0.043 (2) | 0.0328 (18) | 0.0403 (19) | −0.0089 (15) | 0.0068 (16) | −0.0021 (15) |
C22 | 0.048 (2) | 0.0401 (19) | 0.046 (2) | 0.0034 (16) | 0.0119 (18) | 0.0013 (17) |
C23 | 0.066 (3) | 0.041 (2) | 0.041 (2) | −0.0026 (19) | 0.0063 (19) | 0.0072 (17) |
C24 | 0.055 (2) | 0.048 (2) | 0.046 (2) | −0.0137 (19) | 0.0148 (18) | 0.0010 (18) |
C25 | 0.046 (2) | 0.058 (3) | 0.073 (3) | −0.0058 (19) | 0.021 (2) | 0.006 (2) |
C26 | 0.041 (2) | 0.053 (2) | 0.057 (2) | −0.0028 (18) | 0.0053 (18) | 0.0143 (18) |
C27 | 0.080 (3) | 0.079 (3) | 0.070 (3) | −0.018 (3) | 0.024 (2) | 0.012 (2) |
Geometric parameters (Å, º) top
S1—O1 | 1.429 (3) | C11—H11A | 0.97 |
S1—O2 | 1.431 (3) | C11—H11B | 0.97 |
S1—N1 | 1.658 (3) | C12—C13 | 1.365 (5) |
S1—C21 | 1.761 (3) | C12—C17 | 1.375 (5) |
Cl1—C15 | 1.732 (4) | C13—C14 | 1.387 (5) |
Cl2—C14 | 1.707 (4) | C13—H13 | 0.93 |
Cl2'—C16 | 1.575 (9) | C14—C15 | 1.373 (6) |
N1—C10 | 1.493 (4) | C14—H14 | 0.93 |
N1—C2 | 1.495 (4) | C15—C16 | 1.367 (6) |
C2—C10 | 1.481 (4) | C16—C17 | 1.381 (5) |
C2—C3 | 1.526 (4) | C16—H16 | 0.93 |
C2—H2 | 0.98 | C17—H17 | 0.93 |
C3—C11 | 1.539 (4) | C21—C26 | 1.375 (5) |
C3—C4 | 1.548 (4) | C21—C22 | 1.378 (5) |
C3—H3 | 0.98 | C22—C23 | 1.376 (5) |
C4—C5 | 1.507 (4) | C22—H22 | 0.93 |
C4—C8 | 1.548 (4) | C23—C24 | 1.373 (5) |
C4—H4 | 0.98 | C23—H23 | 0.93 |
C5—O3 | 1.209 (4) | C24—C25 | 1.387 (5) |
C5—N6 | 1.401 (4) | C24—C27 | 1.513 (5) |
N6—C7 | 1.402 (4) | C25—C26 | 1.382 (5) |
N6—C12 | 1.433 (4) | C25—H25 | 0.93 |
C7—O4 | 1.203 (4) | C26—H26 | 0.93 |
C7—C8 | 1.510 (5) | C27—H27A | 0.96 |
C8—C9 | 1.553 (4) | C27—H27B | 0.96 |
C8—H8 | 0.98 | C27—H27C | 0.96 |
C9—C10 | 1.518 (4) | C27—H27D | 0.96 |
C9—C11 | 1.533 (4) | C27—H27E | 0.96 |
C9—H9 | 0.98 | C27—H27F | 0.96 |
C10—H10 | 0.98 | | |
| | | |
O1—S1—O2 | 117.21 (18) | C13—C12—N6 | 119.2 (3) |
O1—S1—N1 | 105.57 (15) | C17—C12—N6 | 120.4 (3) |
O2—S1—N1 | 112.42 (14) | C12—C13—C14 | 119.6 (4) |
O1—S1—C21 | 110.71 (16) | C12—C13—H13 | 120.2 |
O2—S1—C21 | 108.70 (16) | C14—C13—H13 | 120.2 |
N1—S1—C21 | 101.02 (14) | C15—C14—C13 | 120.2 (4) |
C10—N1—C2 | 59.42 (18) | C15—C14—Cl2 | 120.1 (3) |
C10—N1—S1 | 116.8 (2) | C13—C14—Cl2 | 119.7 (4) |
C2—N1—S1 | 113.8 (2) | C15—C14—H14 | 119.9 |
C10—C2—N1 | 60.22 (19) | C13—C14—H14 | 119.9 |
C10—C2—C3 | 104.7 (3) | C16—C15—C14 | 119.7 (4) |
N1—C2—C3 | 113.1 (3) | C16—C15—Cl1 | 119.8 (4) |
C10—C2—H2 | 121.0 | C14—C15—Cl1 | 120.5 (4) |
N1—C2—H2 | 121.0 | C15—C16—C17 | 120.4 (4) |
C3—C2—H2 | 121.0 | C15—C16—Cl2' | 111.6 (5) |
C2—C3—C11 | 102.6 (3) | C17—C16—Cl2' | 128.0 (5) |
C2—C3—C4 | 104.5 (2) | C15—C16—H16 | 119.9 |
C11—C3—C4 | 99.9 (3) | C17—C16—H16 | 119.8 |
C2—C3—H3 | 115.9 | C12—C17—C16 | 119.7 (4) |
C11—C3—H3 | 115.9 | C12—C17—H17 | 120.2 |
C4—C3—H3 | 115.9 | C16—C17—H17 | 120.2 |
C5—C4—C8 | 105.2 (3) | C26—C21—C22 | 120.6 (3) |
C5—C4—C3 | 115.9 (3) | C26—C21—S1 | 121.2 (3) |
C8—C4—C3 | 103.6 (2) | C22—C21—S1 | 118.1 (3) |
C5—C4—H4 | 110.6 | C23—C22—C21 | 119.2 (3) |
C8—C4—H4 | 110.6 | C23—C22—H22 | 120.4 |
C3—C4—H4 | 110.6 | C21—C22—H22 | 120.4 |
O3—C5—N6 | 124.4 (3) | C24—C23—C22 | 121.7 (3) |
O3—C5—C4 | 127.3 (3) | C24—C23—H23 | 119.2 |
N6—C5—C4 | 108.3 (3) | C22—C23—H23 | 119.2 |
C5—N6—C7 | 113.1 (3) | C23—C24—C25 | 118.1 (3) |
C5—N6—C12 | 124.5 (3) | C23—C24—C27 | 120.6 (4) |
C7—N6—C12 | 122.5 (3) | C25—C24—C27 | 121.3 (4) |
O4—C7—N6 | 124.4 (3) | C26—C25—C24 | 121.2 (4) |
O4—C7—C8 | 127.4 (3) | C26—C25—H25 | 119.4 |
N6—C7—C8 | 108.2 (3) | C24—C25—H25 | 119.4 |
C7—C8—C4 | 105.1 (3) | C21—C26—C25 | 119.1 (4) |
C7—C8—C9 | 117.5 (3) | C21—C26—H26 | 120.4 |
C4—C8—C9 | 103.2 (2) | C25—C26—H26 | 120.4 |
C7—C8—H8 | 110.2 | C24—C27—H27A | 109.5 |
C4—C8—H8 | 110.2 | C24—C27—H27B | 109.5 |
C9—C8—H8 | 110.2 | H27A—C27—H27B | 109.5 |
C10—C9—C11 | 103.1 (2) | C24—C27—H27C | 109.5 |
C10—C9—C8 | 105.8 (2) | H27A—C27—H27C | 109.5 |
C11—C9—C8 | 98.9 (2) | H27B—C27—H27C | 109.5 |
C10—C9—H9 | 115.6 | C24—C27—H27D | 109.5 |
C11—C9—H9 | 115.6 | H27A—C27—H27D | 141.1 |
C8—C9—H9 | 115.6 | H27B—C27—H27D | 56.3 |
C2—C10—N1 | 60.37 (18) | H27C—C27—H27D | 56.3 |
C2—C10—C9 | 105.2 (2) | C24—C27—H27E | 109.5 |
N1—C10—C9 | 112.6 (2) | H27A—C27—H27E | 56.3 |
C2—C10—H10 | 121.0 | H27B—C27—H27E | 141.1 |
N1—C10—H10 | 121.0 | H27C—C27—H27E | 56.3 |
C9—C10—H10 | 121.0 | H27D—C27—H27E | 109.5 |
C9—C11—C3 | 95.1 (2) | C24—C27—H27F | 109.5 |
C9—C11—H11A | 112.7 | H27A—C27—H27F | 56.3 |
C3—C11—H11A | 112.7 | H27B—C27—H27F | 56.3 |
C9—C11—H11B | 112.7 | H27C—C27—H27F | 141.1 |
C3—C11—H11B | 112.7 | H27D—C27—H27F | 109.5 |
H11A—C11—H11B | 110.2 | H27E—C27—H27F | 109.5 |
C13—C12—C17 | 120.3 (3) | | |
| | | |
O1—S1—N1—C10 | −158.3 (2) | S1—N1—C10—C9 | −161.8 (2) |
O2—S1—N1—C10 | −29.4 (3) | C11—C9—C10—C2 | 31.8 (3) |
C21—S1—N1—C10 | 86.3 (2) | C8—C9—C10—C2 | −71.6 (3) |
O1—S1—N1—C2 | −91.9 (2) | C11—C9—C10—N1 | −32.0 (3) |
O2—S1—N1—C2 | 37.0 (3) | C8—C9—C10—N1 | −135.4 (2) |
C21—S1—N1—C2 | 152.7 (2) | C10—C9—C11—C3 | −49.8 (3) |
S1—N1—C2—C10 | −108.2 (2) | C8—C9—C11—C3 | 58.8 (3) |
C10—N1—C2—C3 | −94.2 (3) | C2—C3—C11—C9 | 50.2 (3) |
S1—N1—C2—C3 | 157.6 (2) | C4—C3—C11—C9 | −57.2 (3) |
C10—C2—C3—C11 | −33.0 (3) | C5—N6—C12—C13 | 51.7 (5) |
N1—C2—C3—C11 | 30.5 (3) | C7—N6—C12—C13 | −128.9 (4) |
C10—C2—C3—C4 | 70.9 (3) | C5—N6—C12—C17 | −130.4 (4) |
N1—C2—C3—C4 | 134.4 (3) | C7—N6—C12—C17 | 49.0 (5) |
C2—C3—C4—C5 | 42.3 (3) | C17—C12—C13—C14 | −0.2 (6) |
C11—C3—C4—C5 | 148.3 (3) | N6—C12—C13—C14 | 177.7 (4) |
C2—C3—C4—C8 | −72.3 (3) | C12—C13—C14—C15 | −1.8 (7) |
C11—C3—C4—C8 | 33.6 (3) | C12—C13—C14—Cl2 | 178.5 (3) |
C8—C4—C5—O3 | 173.1 (3) | C13—C14—C15—C16 | 2.4 (7) |
C3—C4—C5—O3 | 59.3 (4) | Cl2—C14—C15—C16 | −177.9 (4) |
C8—C4—C5—N6 | −4.8 (3) | C13—C14—C15—Cl1 | −176.6 (4) |
C3—C4—C5—N6 | −118.6 (3) | Cl2—C14—C15—Cl1 | 3.1 (6) |
O3—C5—N6—C7 | −174.5 (3) | C14—C15—C16—C17 | −1.0 (7) |
C4—C5—N6—C7 | 3.4 (4) | Cl1—C15—C16—C17 | 178.0 (3) |
O3—C5—N6—C12 | 4.9 (5) | C14—C15—C16—Cl2' | −179.6 (6) |
C4—C5—N6—C12 | −177.1 (3) | Cl1—C15—C16—Cl2' | −0.6 (7) |
C5—N6—C7—O4 | −179.8 (3) | C13—C12—C17—C16 | 1.6 (6) |
C12—N6—C7—O4 | 0.8 (5) | N6—C12—C17—C16 | −176.3 (3) |
C5—N6—C7—C8 | −0.5 (4) | C15—C16—C17—C12 | −0.9 (6) |
C12—N6—C7—C8 | −179.9 (3) | Cl2'—C16—C17—C12 | 177.4 (6) |
O4—C7—C8—C4 | 176.7 (3) | O1—S1—C21—C26 | −66.2 (3) |
N6—C7—C8—C4 | −2.5 (3) | O2—S1—C21—C26 | 163.7 (3) |
O4—C7—C8—C9 | −69.4 (5) | N1—S1—C21—C26 | 45.3 (3) |
N6—C7—C8—C9 | 111.4 (3) | O1—S1—C21—C22 | 113.4 (3) |
C5—C4—C8—C7 | 4.4 (3) | O2—S1—C21—C22 | −16.7 (3) |
C3—C4—C8—C7 | 126.5 (3) | N1—S1—C21—C22 | −135.2 (3) |
C5—C4—C8—C9 | −119.2 (3) | C26—C21—C22—C23 | 1.7 (5) |
C3—C4—C8—C9 | 2.9 (3) | S1—C21—C22—C23 | −177.9 (3) |
C7—C8—C9—C10 | −47.0 (3) | C21—C22—C23—C24 | −1.2 (6) |
C4—C8—C9—C10 | 68.0 (3) | C22—C23—C24—C25 | −0.8 (6) |
C7—C8—C9—C11 | −153.4 (3) | C22—C23—C24—C27 | 179.5 (4) |
C4—C8—C9—C11 | −38.4 (3) | C23—C24—C25—C26 | 2.3 (6) |
C3—C2—C10—N1 | 108.5 (3) | C27—C24—C25—C26 | −178.0 (4) |
N1—C2—C10—C9 | −107.7 (3) | C22—C21—C26—C25 | −0.3 (5) |
C3—C2—C10—C9 | 0.8 (3) | S1—C21—C26—C25 | 179.3 (3) |
S1—N1—C10—C2 | 103.1 (2) | C24—C25—C26—C21 | −1.8 (6) |
C2—N1—C10—C9 | 95.2 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O4i | 0.98 | 2.47 | 3.440 (4) | 170 |
C9—H9···O1ii | 0.98 | 2.57 | 3.317 (4) | 134 |
C13—H13···O1iii | 0.93 | 2.41 | 3.253 (5) | 150 |
C17—H17···O3ii | 0.93 | 2.55 | 3.451 (5) | 164 |
C22—H22···O2iv | 0.93 | 2.45 | 3.097 (4) | 127 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, −y, −z+1. |
(II) 4-(4-chlorophenyl)-9-(4-methylphenylsulfonyl)-4,9- diazatetracyclo[5.3.1.0
2,6.0
8,10]undecane-3,5-dione
top
Crystal data top
C22H19ClN2O4S | Z = 2 |
Mr = 442.90 | F(000) = 460 |
Triclinic, P1 | Dx = 1.449 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.975 (2) Å | Cell parameters from 25 reflections |
b = 10.167 (5) Å | θ = 8.6–17.6° |
c = 12.876 (1) Å | µ = 0.32 mm−1 |
α = 105.06 (2)° | T = 293 K |
β = 109.89 (2)° | Irregular block, colourless |
γ = 100.97 (3)° | 0.43 × 0.40 × 0.36 mm |
V = 1015.4 (6) Å3 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 1.8° |
Graphite monochromator | h = −10→10 |
ω/2θ scans | k = −11→12 |
3941 measured reflections | l = −15→0 |
3764 independent reflections | 3 standard reflections every 200 reflections |
3118 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0472P)2 + 0.3187P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3764 reflections | Δρmax = 0.24 e Å−3 |
273 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.027 (2) |
Crystal data top
C22H19ClN2O4S | γ = 100.97 (3)° |
Mr = 442.90 | V = 1015.4 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.975 (2) Å | Mo Kα radiation |
b = 10.167 (5) Å | µ = 0.32 mm−1 |
c = 12.876 (1) Å | T = 293 K |
α = 105.06 (2)° | 0.43 × 0.40 × 0.36 mm |
β = 109.89 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
3941 measured reflections | 3 standard reflections every 200 reflections |
3764 independent reflections | intensity decay: 1% |
3118 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.24 e Å−3 |
3764 reflections | Δρmin = −0.26 e Å−3 |
273 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.16108 (5) | 0.38633 (5) | 0.17523 (4) | 0.04477 (15) | |
O1 | 0.01990 (17) | 0.43054 (17) | 0.12292 (14) | 0.0661 (4) | |
O2 | 0.15124 (18) | 0.30080 (15) | 0.24661 (13) | 0.0586 (4) | |
Cl1 | 0.98717 (8) | 0.34187 (7) | 0.62471 (5) | 0.0712 (2) | |
N1 | 0.21359 (16) | 0.29367 (14) | 0.07313 (12) | 0.0371 (3) | |
C2 | 0.0660 (2) | 0.18945 (19) | −0.03435 (16) | 0.0437 (4) | |
H2 | −0.0467 | 0.1793 | −0.0381 | 0.052* | |
C3 | 0.1022 (2) | 0.06611 (19) | −0.10833 (15) | 0.0455 (4) | |
H3 | 0.0188 | −0.0275 | −0.1373 | 0.055* | |
C4 | 0.2847 (2) | 0.06683 (18) | −0.05316 (16) | 0.0432 (4) | |
H4 | 0.2983 | −0.0147 | −0.1054 | 0.052* | |
C5 | 0.3653 (2) | 0.07127 (18) | 0.07114 (16) | 0.0407 (4) | |
O3 | 0.32640 (17) | −0.01745 (15) | 0.11178 (13) | 0.0603 (4) | |
N6 | 0.50576 (16) | 0.19196 (15) | 0.13243 (13) | 0.0370 (3) | |
C7 | 0.5095 (2) | 0.28596 (19) | 0.06819 (16) | 0.0402 (4) | |
O4 | 0.60324 (17) | 0.40581 (15) | 0.11014 (13) | 0.0587 (4) | |
C8 | 0.3848 (2) | 0.20514 (19) | −0.05676 (16) | 0.0440 (4) | |
H8 | 0.4443 | 0.1802 | −0.1065 | 0.053* | |
C9 | 0.2503 (2) | 0.2675 (2) | −0.11784 (16) | 0.0478 (4) | |
H9 | 0.2858 | 0.3337 | −0.1544 | 0.057* | |
C10 | 0.1617 (2) | 0.32069 (19) | −0.04102 (16) | 0.0435 (4) | |
H10 | 0.1129 | 0.3977 | −0.0496 | 0.052* | |
C11 | 0.1128 (3) | 0.1258 (2) | −0.20567 (17) | 0.0587 (5) | |
H11A | 0.0098 | 0.1407 | −0.2498 | 0.070* | |
H11B | 0.1490 | 0.0676 | −0.2590 | 0.070* | |
C12 | 0.6191 (2) | 0.22750 (17) | 0.25190 (15) | 0.0361 (4) | |
C13 | 0.5638 (2) | 0.2101 (2) | 0.33675 (17) | 0.0450 (4) | |
H13 | 0.4504 | 0.1750 | 0.3167 | 0.054* | |
C14 | 0.6771 (2) | 0.2448 (2) | 0.45135 (18) | 0.0503 (5) | |
H14 | 0.6404 | 0.2329 | 0.5087 | 0.060* | |
C15 | 0.8452 (2) | 0.2972 (2) | 0.48032 (16) | 0.0464 (4) | |
C16 | 0.9009 (2) | 0.3152 (2) | 0.39598 (17) | 0.0473 (4) | |
H16 | 1.0143 | 0.3506 | 0.4162 | 0.057* | |
C17 | 0.7882 (2) | 0.28082 (19) | 0.28178 (16) | 0.0423 (4) | |
H17 | 0.8253 | 0.2932 | 0.2247 | 0.051* | |
C21 | 0.3377 (2) | 0.53810 (19) | 0.25751 (16) | 0.0418 (4) | |
C22 | 0.4666 (2) | 0.5314 (2) | 0.35034 (19) | 0.0529 (5) | |
H22 | 0.4620 | 0.4467 | 0.3658 | 0.063* | |
C23 | 0.6023 (2) | 0.6515 (2) | 0.4200 (2) | 0.0600 (6) | |
H23 | 0.6892 | 0.6470 | 0.4825 | 0.072* | |
C24 | 0.6118 (3) | 0.7784 (2) | 0.3987 (2) | 0.0565 (5) | |
C25 | 0.4814 (3) | 0.7825 (2) | 0.3044 (2) | 0.0583 (5) | |
H25 | 0.4867 | 0.8671 | 0.2886 | 0.070* | |
C26 | 0.3438 (3) | 0.6635 (2) | 0.23312 (18) | 0.0513 (5) | |
H26 | 0.2571 | 0.6676 | 0.1702 | 0.062* | |
C27 | 0.7591 (3) | 0.9093 (3) | 0.4793 (3) | 0.0876 (8) | |
H27A | 0.7473 | 0.9500 | 0.5511 | 0.131* | |
H27B | 0.7643 | 0.9784 | 0.4410 | 0.131* | |
H27C | 0.8595 | 0.8828 | 0.4971 | 0.131* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0332 (2) | 0.0431 (3) | 0.0551 (3) | 0.01012 (18) | 0.0199 (2) | 0.0113 (2) |
O1 | 0.0382 (7) | 0.0698 (10) | 0.0807 (11) | 0.0257 (7) | 0.0193 (7) | 0.0118 (8) |
O2 | 0.0590 (9) | 0.0526 (8) | 0.0657 (9) | 0.0041 (7) | 0.0367 (7) | 0.0177 (7) |
Cl1 | 0.0780 (4) | 0.0752 (4) | 0.0462 (3) | 0.0208 (3) | 0.0080 (3) | 0.0248 (3) |
N1 | 0.0299 (7) | 0.0342 (7) | 0.0417 (8) | 0.0069 (6) | 0.0111 (6) | 0.0118 (6) |
C2 | 0.0296 (8) | 0.0405 (9) | 0.0476 (10) | 0.0047 (7) | 0.0036 (7) | 0.0154 (8) |
C3 | 0.0425 (10) | 0.0333 (9) | 0.0402 (10) | 0.0003 (7) | 0.0019 (8) | 0.0094 (7) |
C4 | 0.0460 (10) | 0.0323 (9) | 0.0444 (10) | 0.0104 (8) | 0.0152 (8) | 0.0082 (7) |
C5 | 0.0338 (9) | 0.0331 (9) | 0.0513 (10) | 0.0102 (7) | 0.0129 (8) | 0.0150 (8) |
O3 | 0.0464 (8) | 0.0490 (8) | 0.0722 (10) | −0.0009 (6) | 0.0072 (7) | 0.0351 (7) |
N6 | 0.0301 (7) | 0.0358 (7) | 0.0447 (8) | 0.0085 (6) | 0.0142 (6) | 0.0160 (6) |
C7 | 0.0353 (9) | 0.0400 (9) | 0.0488 (10) | 0.0097 (7) | 0.0201 (8) | 0.0187 (8) |
O4 | 0.0499 (8) | 0.0464 (8) | 0.0654 (9) | −0.0026 (6) | 0.0114 (7) | 0.0264 (7) |
C8 | 0.0485 (10) | 0.0440 (10) | 0.0409 (10) | 0.0111 (8) | 0.0227 (8) | 0.0134 (8) |
C9 | 0.0545 (11) | 0.0440 (10) | 0.0380 (9) | 0.0062 (8) | 0.0128 (8) | 0.0185 (8) |
C10 | 0.0373 (9) | 0.0367 (9) | 0.0467 (10) | 0.0091 (7) | 0.0047 (8) | 0.0178 (8) |
C11 | 0.0664 (13) | 0.0502 (12) | 0.0375 (10) | 0.0063 (10) | 0.0043 (9) | 0.0123 (9) |
C12 | 0.0322 (8) | 0.0336 (8) | 0.0433 (9) | 0.0122 (7) | 0.0152 (7) | 0.0140 (7) |
C13 | 0.0381 (9) | 0.0510 (11) | 0.0559 (11) | 0.0175 (8) | 0.0251 (9) | 0.0239 (9) |
C14 | 0.0580 (12) | 0.0580 (12) | 0.0514 (11) | 0.0260 (10) | 0.0308 (10) | 0.0277 (9) |
C15 | 0.0512 (11) | 0.0426 (10) | 0.0422 (10) | 0.0178 (8) | 0.0134 (8) | 0.0150 (8) |
C16 | 0.0354 (9) | 0.0489 (10) | 0.0490 (11) | 0.0083 (8) | 0.0121 (8) | 0.0147 (8) |
C17 | 0.0353 (9) | 0.0461 (10) | 0.0442 (10) | 0.0093 (7) | 0.0180 (8) | 0.0139 (8) |
C21 | 0.0387 (9) | 0.0384 (9) | 0.0477 (10) | 0.0117 (7) | 0.0209 (8) | 0.0101 (8) |
C22 | 0.0450 (10) | 0.0402 (10) | 0.0678 (13) | 0.0156 (8) | 0.0169 (9) | 0.0168 (9) |
C23 | 0.0399 (10) | 0.0544 (12) | 0.0700 (14) | 0.0136 (9) | 0.0114 (10) | 0.0133 (10) |
C24 | 0.0510 (12) | 0.0477 (11) | 0.0651 (13) | 0.0053 (9) | 0.0316 (11) | 0.0076 (10) |
C25 | 0.0770 (15) | 0.0401 (10) | 0.0640 (13) | 0.0097 (10) | 0.0396 (12) | 0.0198 (9) |
C26 | 0.0608 (12) | 0.0482 (11) | 0.0477 (11) | 0.0171 (9) | 0.0234 (9) | 0.0196 (9) |
C27 | 0.0724 (17) | 0.0571 (15) | 0.098 (2) | −0.0093 (12) | 0.0284 (15) | 0.0020 (14) |
Geometric parameters (Å, º) top
S1—O2 | 1.4318 (15) | C10—H10 | 0.98 |
S1—O1 | 1.4334 (15) | C11—H11A | 0.97 |
S1—N1 | 1.6688 (15) | C11—H11B | 0.97 |
S1—C21 | 1.759 (2) | C12—C13 | 1.381 (2) |
Cl1—C15 | 1.737 (2) | C12—C17 | 1.388 (2) |
N1—C10 | 1.498 (2) | C13—C14 | 1.381 (3) |
N1—C2 | 1.500 (2) | C13—H13 | 0.93 |
C2—C10 | 1.483 (3) | C14—C15 | 1.381 (3) |
C2—C3 | 1.526 (3) | C14—H14 | 0.93 |
C2—H2 | 0.98 | C15—C16 | 1.378 (3) |
C3—C4 | 1.546 (3) | C16—C17 | 1.376 (3) |
C3—C11 | 1.550 (3) | C16—H16 | 0.93 |
C3—H3 | 0.98 | C17—H17 | 0.93 |
C4—C5 | 1.500 (3) | C21—C22 | 1.379 (3) |
C4—C8 | 1.539 (3) | C21—C26 | 1.386 (3) |
C4—H4 | 0.98 | C22—C23 | 1.379 (3) |
C5—O3 | 1.208 (2) | C22—H22 | 0.93 |
C5—N6 | 1.396 (2) | C23—C24 | 1.380 (3) |
N6—C7 | 1.420 (2) | C23—H23 | 0.93 |
N6—C12 | 1.428 (2) | C24—C25 | 1.387 (3) |
C7—O4 | 1.201 (2) | C24—C27 | 1.508 (3) |
C7—C8 | 1.501 (3) | C25—C26 | 1.384 (3) |
C8—C9 | 1.543 (3) | C25—H25 | 0.93 |
C8—H8 | 0.98 | C26—H26 | 0.93 |
C9—C10 | 1.525 (3) | C27—H27A | 0.96 |
C9—C11 | 1.551 (3) | C27—H27B | 0.96 |
C9—H9 | 0.98 | C27—H27C | 0.96 |
| | | |
O2—S1—O1 | 118.64 (10) | C2—C10—H10 | 120.5 |
O2—S1—N1 | 105.22 (8) | N1—C10—H10 | 120.5 |
O1—S1—N1 | 111.40 (9) | C9—C10—H10 | 120.5 |
O2—S1—C21 | 108.83 (9) | C3—C11—C9 | 94.45 (14) |
O1—S1—C21 | 109.13 (10) | C3—C11—H11A | 112.8 |
N1—S1—C21 | 102.35 (8) | C9—C11—H11A | 112.8 |
C10—N1—C2 | 59.29 (11) | C3—C11—H11B | 112.8 |
C10—N1—S1 | 116.28 (11) | C9—C11—H11B | 112.8 |
C2—N1—S1 | 113.05 (11) | H11A—C11—H11B | 110.3 |
C10—C2—N1 | 60.32 (11) | C13—C12—C17 | 120.11 (16) |
C10—C2—C3 | 105.39 (16) | C13—C12—N6 | 121.51 (15) |
N1—C2—C3 | 115.28 (14) | C17—C12—N6 | 118.38 (15) |
C10—C2—H2 | 120.1 | C14—C13—C12 | 119.93 (17) |
N1—C2—H2 | 120.1 | C14—C13—H13 | 120.0 |
C3—C2—H2 | 120.1 | C12—C13—H13 | 120.0 |
C2—C3—C4 | 112.99 (14) | C15—C14—C13 | 119.63 (18) |
C2—C3—C11 | 98.77 (15) | C15—C14—H14 | 120.2 |
C4—C3—C11 | 98.48 (16) | C13—C14—H14 | 120.2 |
C2—C3—H3 | 114.8 | C16—C15—C14 | 120.63 (17) |
C4—C3—H3 | 114.8 | C16—C15—Cl1 | 119.87 (15) |
C11—C3—H3 | 114.8 | C14—C15—Cl1 | 119.50 (15) |
C5—C4—C8 | 105.68 (14) | C17—C16—C15 | 119.84 (17) |
C5—C4—C3 | 122.04 (15) | C17—C16—H16 | 120.1 |
C8—C4—C3 | 103.57 (14) | C15—C16—H16 | 120.1 |
C5—C4—H4 | 108.3 | C16—C17—C12 | 119.85 (17) |
C8—C4—H4 | 108.3 | C16—C17—H17 | 120.1 |
C3—C4—H4 | 108.3 | C12—C17—H17 | 120.1 |
O3—C5—N6 | 124.24 (17) | C22—C21—C26 | 120.82 (18) |
O3—C5—C4 | 127.44 (16) | C22—C21—S1 | 118.41 (15) |
N6—C5—C4 | 108.11 (15) | C26—C21—S1 | 120.71 (15) |
C5—N6—C7 | 111.87 (14) | C23—C22—C21 | 119.37 (19) |
C5—N6—C12 | 124.13 (14) | C23—C22—H22 | 120.3 |
C7—N6—C12 | 123.41 (14) | C21—C22—H22 | 120.3 |
O4—C7—N6 | 123.58 (17) | C22—C23—C24 | 121.3 (2) |
O4—C7—C8 | 128.80 (17) | C22—C23—H23 | 119.3 |
N6—C7—C8 | 107.56 (14) | C24—C23—H23 | 119.3 |
C7—C8—C4 | 104.91 (15) | C23—C24—C25 | 118.37 (19) |
C7—C8—C9 | 120.57 (15) | C23—C24—C27 | 120.0 (2) |
C4—C8—C9 | 104.02 (14) | C25—C24—C27 | 121.6 (2) |
C7—C8—H8 | 108.9 | C26—C25—C24 | 121.5 (2) |
C4—C8—H8 | 108.9 | C26—C25—H25 | 119.3 |
C9—C8—H8 | 108.9 | C24—C25—H25 | 119.3 |
C10—C9—C8 | 112.10 (14) | C25—C26—C21 | 118.6 (2) |
C10—C9—C11 | 98.98 (16) | C25—C26—H26 | 120.7 |
C8—C9—C11 | 99.14 (15) | C21—C26—H26 | 120.7 |
C10—C9—H9 | 114.8 | C24—C27—H27A | 109.5 |
C8—C9—H9 | 114.8 | C24—C27—H27B | 109.5 |
C11—C9—H9 | 114.8 | H27A—C27—H27B | 109.5 |
C2—C10—N1 | 60.39 (11) | C24—C27—H27C | 109.5 |
C2—C10—C9 | 104.75 (15) | H27A—C27—H27C | 109.5 |
N1—C10—C9 | 114.59 (14) | H27B—C27—H27C | 109.5 |
| | | |
O2—S1—N1—C10 | 153.97 (12) | C8—C9—C10—C2 | −67.60 (18) |
O1—S1—N1—C10 | 24.16 (14) | C11—C9—C10—C2 | 36.14 (17) |
C21—S1—N1—C10 | −92.33 (13) | C8—C9—C10—N1 | −3.8 (2) |
O2—S1—N1—C2 | 88.10 (13) | C11—C9—C10—N1 | 99.95 (16) |
O1—S1—N1—C2 | −41.70 (14) | C2—C3—C11—C9 | 55.94 (17) |
C21—S1—N1—C2 | −158.19 (12) | C4—C3—C11—C9 | −59.06 (17) |
S1—N1—C2—C10 | 107.87 (13) | C10—C9—C11—C3 | −56.47 (17) |
C10—N1—C2—C3 | 93.93 (18) | C8—C9—C11—C3 | 57.81 (17) |
S1—N1—C2—C3 | −158.20 (13) | C5—N6—C12—C13 | −40.5 (2) |
C10—C2—C3—C4 | 67.77 (18) | C7—N6—C12—C13 | 129.92 (18) |
N1—C2—C3—C4 | 3.7 (2) | C5—N6—C12—C17 | 139.57 (17) |
C10—C2—C3—C11 | −35.39 (17) | C7—N6—C12—C17 | −50.0 (2) |
N1—C2—C3—C11 | −99.41 (17) | C17—C12—C13—C14 | −0.5 (3) |
C2—C3—C4—C5 | 53.6 (2) | N6—C12—C13—C14 | 179.61 (16) |
C11—C3—C4—C5 | 156.92 (16) | C12—C13—C14—C15 | 0.2 (3) |
C2—C3—C4—C8 | −65.05 (19) | C13—C14—C15—C16 | 0.0 (3) |
C11—C3—C4—C8 | 38.29 (17) | C13—C14—C15—Cl1 | 179.58 (14) |
C8—C4—C5—O3 | −179.35 (18) | C14—C15—C16—C17 | 0.1 (3) |
C3—C4—C5—O3 | 63.0 (3) | Cl1—C15—C16—C17 | −179.54 (14) |
C8—C4—C5—N6 | −4.42 (18) | C15—C16—C17—C12 | −0.3 (3) |
C3—C4—C5—N6 | −122.02 (17) | C13—C12—C17—C16 | 0.5 (3) |
O3—C5—N6—C7 | −172.88 (17) | N6—C12—C17—C16 | −179.57 (15) |
C4—C5—N6—C7 | 11.99 (19) | O2—S1—C21—C22 | 23.34 (18) |
O3—C5—N6—C12 | −1.5 (3) | O1—S1—C21—C22 | 154.21 (16) |
C4—C5—N6—C12 | −176.63 (14) | N1—S1—C21—C22 | −87.67 (16) |
C5—N6—C7—O4 | 168.04 (17) | O2—S1—C21—C26 | −153.60 (15) |
C12—N6—C7—O4 | −3.4 (3) | O1—S1—C21—C26 | −22.74 (18) |
C5—N6—C7—C8 | −14.64 (19) | N1—S1—C21—C26 | 95.38 (16) |
C12—N6—C7—C8 | 173.90 (14) | C26—C21—C22—C23 | 0.4 (3) |
O4—C7—C8—C4 | −171.94 (19) | S1—C21—C22—C23 | −176.50 (16) |
N6—C7—C8—C4 | 10.93 (18) | C21—C22—C23—C24 | 0.0 (3) |
O4—C7—C8—C9 | −55.3 (3) | C22—C23—C24—C25 | −0.5 (3) |
N6—C7—C8—C9 | 127.57 (16) | C22—C23—C24—C27 | 177.8 (2) |
C5—C4—C8—C7 | −4.00 (18) | C23—C24—C25—C26 | 0.6 (3) |
C3—C4—C8—C7 | 125.40 (15) | C27—C24—C25—C26 | −177.7 (2) |
C5—C4—C8—C9 | −131.51 (15) | C24—C25—C26—C21 | −0.1 (3) |
C3—C4—C8—C9 | −2.12 (17) | C22—C21—C26—C25 | −0.4 (3) |
C7—C8—C9—C10 | −48.3 (2) | S1—C21—C26—C25 | 176.45 (15) |
C4—C8—C9—C10 | 68.79 (18) | N1—C2—C3—C11 | −99.41 (17) |
C7—C8—C9—C11 | −151.95 (16) | N1—C2—C3—C4 | 3.7 (2) |
C4—C8—C9—C11 | −34.85 (18) | C5—C4—C3—C11 | 156.92 (16) |
C3—C2—C10—N1 | −110.67 (14) | C5—C4—C3—C2 | 53.6 (2) |
N1—C2—C10—C9 | 110.20 (15) | N1—C10—C9—C8 | −3.8 (2) |
C3—C2—C10—C9 | −0.47 (17) | N1—C10—C9—C11 | 99.95 (16) |
S1—N1—C10—C2 | −102.40 (13) | C7—C8—C9—C10 | −48.3 (2) |
C2—N1—C10—C9 | −93.56 (17) | C7—C8—C9—C11 | −151.95 (16) |
S1—N1—C10—C9 | 164.05 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 0.98 | 2.43 | 3.289 (2) | 146 |
C9—H9···O4ii | 0.98 | 2.48 | 3.294 (3) | 140 |
C10—H10···O1iii | 0.98 | 2.50 | 3.457 (3) | 166 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C22H18Cl2N2O4S | C22H19ClN2O4S |
Mr | 477.34 | 442.90 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.856 (1), 15.689 (1), 10.727 (1) | 8.975 (2), 10.167 (5), 12.876 (1) |
α, β, γ (°) | 90, 100.27 (1), 90 | 105.06 (2), 109.89 (2), 100.97 (3) |
V (Å3) | 2128.9 (3) | 1015.4 (6) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.32 |
Crystal size (mm) | 0.50 × 0.40 × 0.10 | 0.43 × 0.40 × 0.36 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | – |
Tmin, Tmax | 0.844, 0.934 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3962, 3785, 2300 | 3941, 3764, 3118 |
Rint | 0.028 | 0.013 |
(sin θ/λ)max (Å−1) | 0.596 | 0.605 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.137, 1.03 | 0.036, 0.097, 1.04 |
No. of reflections | 3785 | 3764 |
No. of parameters | 291 | 273 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.46 | 0.24, −0.26 |
Selected geometric parameters (Å, º) for (I) topS1—O1 | 1.429 (3) | N1—C2 | 1.495 (4) |
S1—O2 | 1.431 (3) | C2—C10 | 1.481 (4) |
S1—N1 | 1.658 (3) | C2—C3 | 1.526 (4) |
S1—C21 | 1.761 (3) | C4—C8 | 1.548 (4) |
N1—C10 | 1.493 (4) | | |
| | | |
O1—S1—O2 | 117.21 (18) | C10—N1—S1 | 116.8 (2) |
O1—S1—N1 | 105.57 (15) | C2—N1—S1 | 113.8 (2) |
O2—S1—N1 | 112.42 (14) | C10—C2—N1 | 60.22 (19) |
O1—S1—C21 | 110.71 (16) | C5—N6—C7 | 113.1 (3) |
O2—S1—C21 | 108.70 (16) | C5—N6—C12 | 124.5 (3) |
N1—S1—C21 | 101.02 (14) | C7—N6—C12 | 122.5 (3) |
C10—N1—C2 | 59.42 (18) | C2—C10—N1 | 60.37 (18) |
| | | |
N1—C2—C3—C11 | 30.5 (3) | C2—C3—C4—C8 | −72.3 (3) |
N1—C2—C3—C4 | 134.4 (3) | C4—C8—C9—C10 | 68.0 (3) |
C2—C3—C4—C5 | 42.3 (3) | C7—C8—C9—C11 | −153.4 (3) |
C11—C3—C4—C5 | 148.3 (3) | C8—C9—C10—N1 | −135.4 (2) |
Selected geometric parameters (Å, º) for (II) topS1—O2 | 1.4318 (15) | N1—C2 | 1.500 (2) |
S1—O1 | 1.4334 (15) | C2—C10 | 1.483 (3) |
S1—N1 | 1.6688 (15) | C2—C3 | 1.526 (3) |
S1—C21 | 1.759 (2) | C4—C8 | 1.539 (3) |
N1—C10 | 1.498 (2) | | |
| | | |
O2—S1—O1 | 118.64 (10) | C10—N1—S1 | 116.28 (11) |
O2—S1—N1 | 105.22 (8) | C2—N1—S1 | 113.05 (11) |
O1—S1—N1 | 111.40 (9) | C10—C2—N1 | 60.32 (11) |
O2—S1—C21 | 108.83 (9) | C5—N6—C7 | 111.87 (14) |
O1—S1—C21 | 109.13 (10) | C5—N6—C12 | 124.13 (14) |
N1—S1—C21 | 102.35 (8) | C7—N6—C12 | 123.41 (14) |
C10—N1—C2 | 59.29 (11) | C2—C10—N1 | 60.39 (11) |
| | | |
N1—C2—C3—C4 | 3.7 (2) | C7—C8—C9—C10 | −48.3 (2) |
N1—C2—C3—C11 | −99.41 (17) | C7—C8—C9—C11 | −151.95 (16) |
C2—C3—C4—C5 | 53.6 (2) | C8—C9—C10—N1 | −3.8 (2) |
C11—C3—C4—C5 | 156.92 (16) | C11—C9—C10—N1 | 99.95 (16) |
Maleimides and aziridines are well known for the diversity of their applications in medicinal chemistry. A great number of compounds with an aziridine ring have been synthesized, many of which have shown significant cytotoxicity against some tumour cells, such as mitomycin C, which is a bioreductive alkylating agent used in anticancer therapy (Kim et al., 1996; Kumar et al., 1996). Maleimides have also presented activity against some types of tumour, together with other pharmacological properties such as sedative, hypnotic, antihypertensive and diuretic properties, and in chemotherapy for tuberculosis. An example of this is mitonafide, which is already used as a drug and which has also been used as a model in the development of new drugs with improved effectiveness and reduced adverse effects (Asbury et al., 1994; Cechinel Filho et al., 2003).
In order to obtain additional proof that the products we synthesized are the exo-endo, (I), and endo-endo, (II), imidobenzenesulfonylaziridines, we have determined the molecular and crystal structures of the title compounds by X-ray diffraction and the results are presented here. According to a recent search in the Cambridge Structural Database (CSD, 2003, Version 5.25; Allen, 2002), the title compounds are the first examples of di-substituted norbornane with p-toluenesulfonamide and maleimide groups to be characterized by X-ray diffraction. \sch
Compounds (I) (Fig. 1) and (II) (Fig. 2) show the endo configuration with respect to the maleimide ring [C4/C5/N6/C7/C8], which is essentially planar in both structures. The dihedral angles between the planes of the rings C4/C5/N6/C7/C8 and N1/C2/C10 [54.9 (1)° in (I) and 2.6 (2)° in (II)] clearly indicate the different configurations, exo and endo, respectively, with respect to the aziridine ring (N1/C2/C10). In addition, the torsion angles N1—C2—C3—C11 and C11—C3—C4—C5 (Tables 1 and 2) also confirm the configurations as exo-endo for (I) and endo-endo for (II).
The three-membered aziridine ring is an almost-perfect isosceles triangle in both stereoisomers, with the N1—C2 and N1—C10 bond lengths being equal within experimental error, and the sums of the internal angles are very close to 180° (Tables 1 and 2). The C—N bonds in the aziridine rings are about 0.1 Å longer than those in the maleimide rings. This results from a combination of factors, such as a high level of tension in the three-membered ring, the substitution of the phenylsulfonyl moiety at N1 [due to the electron-withdrawing effect from this group, as described by Govindasamy et al. (1998)] and the hybridization character at atoms N1 and N6. The sums of the angles around N1 [290.0° in (I) and 288.6° in (II)] and N6 [360.1° in (I) and 359.4° in (II)] indicate essentially sp3 and sp2 hybridization, respectively. This is as expected and is in agreement with related structures (Kajfez et al., 2003; Matthews et al., 2001; Yoshihara et al., 1999; Massa et al., 1983). In the norbornane skeletons of both (I) and (II), the C2—C10 bond is a little shorter than the neighbouring C—C bonds (Tables 1 and 2). This should be induced by the restriction imposed by the formation of the aziridine ring and was also observed in the related structures reported by Matthews et al. (2001), and references therein.
The environment around the S atoms in both compounds is best described as a distorted tetrahedron, with angles raging from 101.02 (14) to 118.64 (10)°, as observed in similar structures (Massa et al., 1983; Seshadri et al., 2002). Other geometric parameters show normal values and are within the expected ranges.
The three-dimensional packing of the title compounds is strongly influenced by van der Waals interactions. There is no evidence of π–π stacking involving the phenyl rings. All O atoms in (I) and three O atoms (two from the maleimide ring and one from the sulfonyl moiety) in (II) participate in C—H···O interactions. The geometric parameters of these interactions are available in the archived CIF.