Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010804287X/gd3257sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010804287X/gd3257Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010804287X/gd3257IIsup3.hkl |
CCDC references: 724200; 724201
Compound (I) was prepared from the reaction of 1,7 b-dihydroazireno[1,2-b][1,2]benzisothiazole 3,3-dioxide (180 mg, 1.0 mmol), obtained according to the literature procedure (Dauban & Dodd, 2000, Kiefer et al., 2008), with (R)-naphthylethylamine (2 equivalents, 2.0 mmol, 325 µl) dissolved in tetrahydrofuran (THF). The solution was heated to 333 K and stirred for a period of 18 h with monitoring by thin-layer chromatography until completion. The resulting solution was evaporated on a rotary evaporator. The residue was purified by flash chromatography (silica gel, AcOEt/heptane 3:7) to give a mixture of two diastereoisomers in 25% yield, which were separated by high-pressure liquid chromatography (HPLC; tR1 = 26.8 min; tR2 = 31.7 min; symmetry column 4.6 × 150 mm, 1 ml min-1, H2O + 0.1%HCO2H/CH3CN + 0.1%HCO2H: 80/20). The resulting compounds were transformed into their hydrochloride salts by treatment with MeOH–HCl. White needle-like crystals of the more polar diastereoisomer (corresponding to that having a retention time of 26.8 min) were obtained by slow recrystallization in methanol. 1H NMR (CDCl3, 500 MHz): δ 8.19 (1H, br s), 7.94 (H, d, J = 7.3 Hz), 7.84 (1H, d, J = 7.3 Hz), 7.83 (1H, d, J = 6.5 Hz), 7.73 (1H, d, J = 7.3 Hz), 7.61–7.52 (3H, m), 7.50–7.44 (2H, m), 7.15 (1H, d, J = 6.5 Hz), 5.57 (1H, br s), 4.83 (1H, q, J = 6.6 Hz), 3.84 (1H, t, J = 2.3 Hz), 3.75 (1H, d, J = 15.2 Hz), 3.32 (1H, dd, J1 = 15.2 Hz, J2 = 2.3 Hz), 1.61 (3H, d, J = 6.6 Hz). 13C NMR (CDCl3, 75.5 MHz): δ 139.4, 137.7, 136.1, 134.2, 132.3, 130.5, 129.6, 129.3, 128.2, 126.4, 125.8, 125.7, 124.9, 123.3, 122.3, 53.6, 53.0, 46.2, 24.0. MS (ES+) 375.1, M + Na. HRMS found: 375.1166; C20H20N2NaO2S requires: 375.1143. Compound (II) was prepared according to the same procedure but starting from 4b,5-dihydroazireno[1,2-b]dibenzo[d,f][1,2]thiazepine 7,7-dioxide (75 mg, 0.29 mmol) and (R)-naphthylethylamine (2 equivalents, 0.58 mmol, 95 µl) in THF at 343 K. The residue was purified by flash chromatography (silica gel, AcOEt/heptane 5:5 + 5% NEt3) to give a mixture of two diastereoisomers in 86% yield, which were separated by HPLC (tR1 = 16.5 min; tR2 = 20.7 min; Sunfire column 2, 3 × 150 mm, 0.7 ml min-1, H2O + 0.1%HCO2H /CH3CN + 0.1%HCO2H: 79/21). The resulting compounds were transformed into their hydrochloride salts by treatment with MeOH–HCl. White needle-like crystals of the more polar diastereoisomer (corresponding to that having a retention time of 16.5 min) were obtained by slow recrystallization in methanol. 1H NMR (CDCl3, 500 MHz): δ 8.21 (1H, br s), 8.02 (1H, d, J = 7.6 Hz), 7.92 (1H, d, J = 7.6 Hz), 7.86 (1H, d, J = 7.6 Hz), 7.74 (1H, d, J = 7.6 Hz), 7.57 (1H, t, J = 7.6 Hz), 7.54–7.48 (3H, m), 7.47–7.40 (3H, m), 7.39–7.32 (3H, m), 7.22 (1H, d, J = 7.6 Hz), 4.71 (1H, q, J = 6.0 Hz), 4.14 (1H, br s), 3.02 (1H, br s), 2.91 (1H, br s), 1.56 (3H, d, J = 6.0 Hz). 13C NMR (CDCl3, 75.5 MHz): δ 138.2 (2C), 133.9 (2C), 133.6, 133.0, 130.8 (2C), 129.9 (2C), 129.6, 129.2 (3C), 128.6, 128.5, 126.7, 125.9, 125.7, 125.6, 123.4, 122.1, 54.3, 54.2, 49.7, 21.9. MS (ES+) 429.1, M + H. HRMS found: 429.1667; C26H25N2NaO2S [H24?] requires: 429.1637.
All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.93 (aromatic), 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine) and N—H distances of 0.90 Å (amine), and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms. Exception was made for the sulfonamide H atoms, which were freely refined at the early stage of the refinement to highlight the sp3 character of the sulfonamide N atom, then constrained to ride. Three floating origin restraints were generated automatically by SHELXL97 (Sheldrick, 2008). Friedel opposites were kept unmerged, and the anomalous scattering contribution, albeit weak, of the chloride anions and S atoms [2356 Bijvoet pairs for (I), 3619 for (II)] was exploited to confirm use of the values of the Flack (1983) parameter. The absolute configuration of each compound was assigned by reference to the unchanging (R)-naphthylethylamine chiral centre from the commercial source.
For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).
C20H21N2O2S+·Cl− | Z = 2 |
Mr = 388.90 | F(000) = 408 |
Triclinic, P1 | Dx = 1.356 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.230 (2) Å | Cell parameters from 2751 reflections |
b = 10.927 (2) Å | θ = 1.0–24.1° |
c = 11.633 (3) Å | µ = 0.33 mm−1 |
α = 103.90 (2)° | T = 293 K |
β = 106.62 (3)° | Plate, colourless |
γ = 96.94 (2)° | 0.15 × 0.10 × 0.05 mm |
V = 952.7 (4) Å3 |
Nonius KappaCCD diffractometer | 5771 independent reflections |
Radiation source: fine-focus sealed tube | 4862 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
phi and ω scans | θmax = 25.3°, θmin = 1.9° |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | h = −9→9 |
Tmin = 0.88, Tmax = 0.98 | k = −13→13 |
7330 measured reflections | l = −13→13 |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0361P)2 + 0.1452P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.095 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.18 e Å−3 |
5771 reflections | Δρmin = −0.17 e Å−3 |
472 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.018 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 2356 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.05 (5) |
C20H21N2O2S+·Cl− | γ = 96.94 (2)° |
Mr = 388.90 | V = 952.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.230 (2) Å | Mo Kα radiation |
b = 10.927 (2) Å | µ = 0.33 mm−1 |
c = 11.633 (3) Å | T = 293 K |
α = 103.90 (2)° | 0.15 × 0.10 × 0.05 mm |
β = 106.62 (3)° |
Nonius KappaCCD diffractometer | 5771 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 4862 reflections with I > 2σ(I) |
Tmin = 0.88, Tmax = 0.98 | Rint = 0.025 |
7330 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.095 | Δρmax = 0.18 e Å−3 |
S = 1.02 | Δρmin = −0.17 e Å−3 |
5771 reflections | Absolute structure: Flack (1983), 2356 Friedel pairs |
472 parameters | Absolute structure parameter: 0.05 (5) |
3 restraints |
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. Checkcif output: 220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ···3.41 Ratio 222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ··· 3.43 Ratio 241_ALERT_2_C Check High Ueq as Compared to Neighbors for C19 241_ALERT_2_C Check High Ueq as Compared to Neighbors for C19' 340_ALERT_3_C Low Bond Precision on C—C Bonds (x 1000) Ang ··· 7 410_ALERT_2_C Short Intra H···H Contact H12'.. H21'.. 1.97 A ng. This contact has been checked, but does not appear to be very significant (Alert C). In comparison with the other copy in the asymmetric unit the same contact has a value slightly above 2.0 Å. 234_ALERT_4_C Large Hirshfeld Difference C16 – C17.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C18 – C19.. 0.14 A ng. 234_ALERT_4_C Large Hirshfeld Difference C19 – C20.. 0.13 A ng. 234_ALERT_4_C Large Hirshfeld Difference C7' – C8'.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C17' – C17B.. 0.12 A ng. 234_ALERT_4_C Large Hirshfeld Difference C21' – C21B.. 0.11 A ng. 860_ALERT_3_G Note: Number of Least-Squares Restraints ······. 3 three floating origin restraints were generated automatically by the SHELXL97 program. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.64137 (13) | 0.50685 (9) | 0.35811 (9) | 0.0619 (3) | |
O2 | 0.5323 (4) | −0.0135 (3) | 0.2199 (3) | 0.0710 (8) | |
S1 | 0.49663 (12) | 0.11285 (9) | 0.24750 (8) | 0.0534 (2) | |
N2 | 0.6775 (4) | 0.2155 (3) | 0.3233 (3) | 0.0498 (7) | |
H2 | 0.6643 | 0.3023 | 0.3265 | 0.060* | |
N11 | 0.6859 (3) | 0.3874 (2) | 0.5879 (2) | 0.0381 (6) | |
H11A | 0.5966 | 0.4040 | 0.6149 | 0.046* | |
H11B | 0.6768 | 0.4190 | 0.5221 | 0.046* | |
C3 | 0.7617 (4) | 0.2041 (4) | 0.4497 (3) | 0.0486 (8) | |
H3A | 0.8770 | 0.2579 | 0.4840 | 0.058* | |
H3B | 0.7741 | 0.1157 | 0.4425 | 0.058* | |
C4 | 0.6628 (4) | 0.2427 (3) | 0.5403 (3) | 0.0387 (7) | |
H4 | 0.7120 | 0.2123 | 0.6129 | 0.046* | |
C4A | 0.4708 (4) | 0.1805 (3) | 0.4854 (3) | 0.0410 (7) | |
C5 | 0.3759 (5) | 0.1747 (3) | 0.5659 (3) | 0.0501 (8) | |
H5 | 0.4295 | 0.2127 | 0.6515 | 0.060* | |
C6 | 0.2045 (5) | 0.1139 (4) | 0.5219 (4) | 0.0604 (10) | |
H6 | 0.1432 | 0.1125 | 0.5776 | 0.072* | |
C7 | 0.1233 (5) | 0.0550 (4) | 0.3960 (4) | 0.0685 (12) | |
H7 | 0.0081 | 0.0123 | 0.3670 | 0.082* | |
C8 | 0.2127 (5) | 0.0594 (4) | 0.3121 (4) | 0.0573 (9) | |
H8 | 0.1578 | 0.0216 | 0.2266 | 0.069* | |
C12 | 0.8553 (4) | 0.4646 (3) | 0.6938 (3) | 0.0453 (8) | |
H12 | 0.8231 | 0.5341 | 0.7482 | 0.054* | |
C14 | 0.9326 (4) | 0.3827 (3) | 0.7737 (3) | 0.0458 (8) | |
C15 | 1.0795 (4) | 0.3383 (4) | 0.7653 (4) | 0.0565 (10) | |
H15 | 1.1315 | 0.3597 | 0.7096 | 0.068* | |
C16 | 1.1520 (6) | 0.2622 (4) | 0.8378 (4) | 0.0750 (13) | |
H16 | 1.2526 | 0.2349 | 0.8314 | 0.090* | |
C17 | 1.0778 (8) | 0.2278 (4) | 0.9170 (4) | 0.0852 (16) | |
H17 | 1.1259 | 0.1749 | 0.9634 | 0.102* | |
C18 | 0.8488 (10) | 0.2371 (6) | 1.0154 (5) | 0.114 (2) | |
H18 | 0.8940 | 0.1829 | 1.0612 | 0.137* | |
C19 | 0.7090 (11) | 0.2828 (8) | 1.0301 (5) | 0.132 (3) | |
H19 | 0.6583 | 0.2581 | 1.0851 | 0.158* | |
C20 | 0.6370 (7) | 0.3672 (7) | 0.9643 (5) | 0.110 (2) | |
H20 | 0.5425 | 0.3997 | 0.9777 | 0.132* | |
C21 | 0.7089 (5) | 0.4007 (5) | 0.8799 (4) | 0.0736 (13) | |
H21 | 0.6617 | 0.4551 | 0.8352 | 0.088* | |
C13 | 0.9765 (5) | 0.5283 (4) | 0.6390 (4) | 0.0646 (11) | |
H13A | 0.9228 | 0.5879 | 0.6000 | 0.097* | |
H13B | 1.0009 | 0.4637 | 0.5777 | 0.097* | |
H13C | 1.0825 | 0.5735 | 0.7046 | 0.097* | |
O1 | 0.4047 (4) | 0.1572 (3) | 0.1467 (2) | 0.0797 (9) | |
C8A | 0.3870 (4) | 0.1215 (3) | 0.3584 (3) | 0.0439 (8) | |
C17A | 0.9273 (7) | 0.2708 (4) | 0.9312 (3) | 0.0727 (13) | |
C21A | 0.8546 (4) | 0.3524 (4) | 0.8608 (3) | 0.0550 (10) | |
Cl1' | 0.41359 (11) | 0.52808 (10) | 0.65666 (9) | 0.0609 (3) | |
S1' | 0.73816 (11) | 0.88927 (9) | 0.63088 (9) | 0.0539 (2) | |
O1' | 0.8551 (3) | 0.8273 (3) | 0.7015 (3) | 0.0785 (9) | |
O2' | 0.7986 (3) | 1.0188 (2) | 0.6349 (3) | 0.0679 (7) | |
N2' | 0.6702 (4) | 0.8014 (3) | 0.4864 (3) | 0.0616 (8) | |
H2' | 0.6922 | 0.7198 | 0.4930 | 0.074* | |
N11' | 0.3243 (3) | 0.6224 (2) | 0.4226 (3) | 0.0466 (7) | |
H11C | 0.4099 | 0.5947 | 0.3965 | 0.056* | |
H11D | 0.3306 | 0.6015 | 0.4938 | 0.056* | |
C3' | 0.5037 (6) | 0.8160 (4) | 0.4100 (4) | 0.0659 (11) | |
H3C | 0.4816 | 0.7680 | 0.3234 | 0.079* | |
H3D | 0.5082 | 0.9061 | 0.4139 | 0.079* | |
C4' | 0.3565 (5) | 0.7691 (3) | 0.4524 (3) | 0.0488 (8) | |
H4' | 0.2518 | 0.7915 | 0.4037 | 0.059* | |
C4B | 0.3857 (4) | 0.8316 (3) | 0.5889 (3) | 0.0460 (8) | |
C8B | 0.5505 (4) | 0.8880 (3) | 0.6741 (3) | 0.0453 (8) | |
C5' | 0.2455 (5) | 0.8378 (4) | 0.6330 (4) | 0.0596 (10) | |
H5' | 0.1342 | 0.8004 | 0.5779 | 0.072* | |
C6' | 0.2684 (6) | 0.8984 (4) | 0.7567 (4) | 0.0738 (12) | |
H6' | 0.1732 | 0.9013 | 0.7844 | 0.089* | |
C7' | 0.4329 (6) | 0.9546 (5) | 0.8394 (4) | 0.0733 (12) | |
H7' | 0.4483 | 0.9960 | 0.9227 | 0.088* | |
C8' | 0.5744 (5) | 0.9494 (4) | 0.7986 (4) | 0.0626 (10) | |
H8' | 0.6853 | 0.9869 | 0.8543 | 0.075* | |
C17B | 0.0223 (6) | 0.7098 (4) | 0.0566 (4) | 0.0630 (10) | |
C21B | 0.0173 (5) | 0.6631 (4) | 0.1612 (3) | 0.0560 (9) | |
C12' | 0.1529 (5) | 0.5512 (4) | 0.3246 (3) | 0.0564 (9) | |
H12' | 0.0595 | 0.5779 | 0.3550 | 0.068* | |
C14' | 0.1400 (5) | 0.5905 (4) | 0.2051 (3) | 0.0556 (9) | |
C15' | 0.2552 (5) | 0.5611 (4) | 0.1423 (4) | 0.0703 (11) | |
H15' | 0.3311 | 0.5090 | 0.1681 | 0.084* | |
C16' | 0.2623 (6) | 0.6067 (5) | 0.0414 (4) | 0.0790 (14) | |
H16' | 0.3431 | 0.5865 | 0.0019 | 0.095* | |
C17' | 0.1489 (6) | 0.6815 (5) | 0.0009 (4) | 0.0779 (13) | |
H17' | 0.1560 | 0.7141 | −0.0648 | 0.093* | |
C18' | −0.0995 (7) | 0.7809 (5) | 0.0122 (5) | 0.0898 (15) | |
H18' | −0.0974 | 0.8096 | −0.0566 | 0.108* | |
C19' | −0.2189 (8) | 0.8085 (6) | 0.0665 (6) | 0.1062 (19) | |
H19' | −0.2962 | 0.8583 | 0.0371 | 0.127* | |
C20' | −0.2278 (7) | 0.7631 (6) | 0.1668 (5) | 0.0904 (15) | |
H20' | −0.3132 | 0.7810 | 0.2024 | 0.108* | |
C21' | −0.1148 (5) | 0.6934 (4) | 0.2135 (4) | 0.0681 (11) | |
H21' | −0.1232 | 0.6647 | 0.2810 | 0.082* | |
C13' | 0.1421 (7) | 0.4085 (4) | 0.3101 (4) | 0.0839 (14) | |
H13D | 0.1664 | 0.3941 | 0.3910 | 0.126* | |
H13E | 0.2252 | 0.3791 | 0.2724 | 0.126* | |
H13F | 0.0278 | 0.3621 | 0.2578 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0850 (7) | 0.0528 (6) | 0.0617 (6) | 0.0266 (5) | 0.0303 (5) | 0.0277 (5) |
O2 | 0.108 (2) | 0.0493 (16) | 0.0648 (17) | 0.0208 (15) | 0.0466 (17) | 0.0073 (13) |
S1 | 0.0722 (6) | 0.0520 (6) | 0.0394 (5) | 0.0153 (5) | 0.0206 (4) | 0.0152 (4) |
N2 | 0.0632 (18) | 0.0454 (17) | 0.0506 (17) | 0.0147 (14) | 0.0290 (15) | 0.0174 (14) |
N11 | 0.0346 (13) | 0.0446 (16) | 0.0400 (15) | 0.0126 (12) | 0.0154 (11) | 0.0148 (12) |
C3 | 0.0471 (19) | 0.050 (2) | 0.053 (2) | 0.0175 (16) | 0.0215 (17) | 0.0120 (17) |
C4 | 0.0366 (15) | 0.0394 (18) | 0.0412 (18) | 0.0101 (13) | 0.0109 (14) | 0.0149 (15) |
C4A | 0.0448 (18) | 0.0367 (18) | 0.0442 (19) | 0.0113 (15) | 0.0165 (16) | 0.0125 (15) |
C5 | 0.060 (2) | 0.045 (2) | 0.052 (2) | 0.0126 (17) | 0.0279 (18) | 0.0125 (17) |
C6 | 0.061 (2) | 0.051 (2) | 0.077 (3) | 0.0100 (19) | 0.037 (2) | 0.014 (2) |
C7 | 0.045 (2) | 0.055 (2) | 0.095 (3) | 0.0009 (18) | 0.021 (2) | 0.007 (2) |
C8 | 0.051 (2) | 0.054 (2) | 0.056 (2) | 0.0126 (17) | 0.0088 (18) | 0.0047 (19) |
C12 | 0.0397 (17) | 0.0454 (19) | 0.047 (2) | 0.0075 (15) | 0.0103 (15) | 0.0114 (16) |
C14 | 0.0386 (17) | 0.049 (2) | 0.0412 (19) | 0.0056 (15) | 0.0044 (15) | 0.0085 (16) |
C15 | 0.0437 (19) | 0.061 (2) | 0.055 (2) | 0.0143 (18) | 0.0076 (17) | 0.0074 (19) |
C16 | 0.072 (3) | 0.063 (3) | 0.067 (3) | 0.025 (2) | −0.009 (2) | 0.010 (3) |
C17 | 0.112 (4) | 0.055 (3) | 0.053 (3) | 0.012 (3) | −0.025 (3) | 0.017 (2) |
C18 | 0.153 (6) | 0.106 (5) | 0.041 (3) | −0.052 (4) | −0.001 (3) | 0.020 (3) |
C19 | 0.158 (7) | 0.144 (6) | 0.049 (3) | −0.082 (6) | 0.031 (4) | 0.007 (3) |
C20 | 0.088 (4) | 0.158 (6) | 0.060 (3) | −0.037 (4) | 0.035 (3) | 0.003 (4) |
C21 | 0.053 (2) | 0.106 (4) | 0.047 (2) | −0.011 (2) | 0.0181 (19) | 0.006 (2) |
C13 | 0.051 (2) | 0.064 (3) | 0.077 (3) | −0.0001 (19) | 0.016 (2) | 0.029 (2) |
O1 | 0.099 (2) | 0.094 (2) | 0.0492 (16) | 0.0189 (18) | 0.0152 (15) | 0.0382 (16) |
C8A | 0.0486 (19) | 0.0398 (18) | 0.044 (2) | 0.0150 (15) | 0.0126 (16) | 0.0129 (16) |
C17A | 0.095 (3) | 0.061 (3) | 0.032 (2) | −0.020 (3) | −0.006 (2) | 0.010 (2) |
C21A | 0.048 (2) | 0.066 (2) | 0.0345 (19) | −0.0105 (17) | 0.0039 (16) | 0.0080 (18) |
Cl1' | 0.0580 (5) | 0.0753 (7) | 0.0694 (6) | 0.0346 (5) | 0.0308 (5) | 0.0349 (5) |
S1' | 0.0475 (5) | 0.0472 (5) | 0.0665 (6) | 0.0090 (4) | 0.0156 (4) | 0.0194 (5) |
O1' | 0.0545 (16) | 0.087 (2) | 0.107 (2) | 0.0309 (15) | 0.0229 (16) | 0.0481 (19) |
O2' | 0.0646 (15) | 0.0443 (15) | 0.0832 (19) | −0.0052 (12) | 0.0154 (14) | 0.0157 (14) |
N2' | 0.072 (2) | 0.0456 (18) | 0.066 (2) | 0.0016 (15) | 0.0313 (18) | 0.0094 (16) |
N11' | 0.0525 (16) | 0.0345 (15) | 0.0442 (16) | 0.0073 (12) | 0.0039 (13) | 0.0108 (13) |
C3' | 0.101 (3) | 0.043 (2) | 0.050 (2) | 0.001 (2) | 0.023 (2) | 0.0168 (18) |
C4' | 0.060 (2) | 0.0350 (18) | 0.0432 (19) | 0.0112 (16) | 0.0019 (17) | 0.0134 (16) |
C4B | 0.0464 (18) | 0.0359 (18) | 0.049 (2) | 0.0092 (15) | 0.0058 (16) | 0.0115 (15) |
C8B | 0.0458 (18) | 0.0403 (18) | 0.045 (2) | 0.0101 (15) | 0.0082 (16) | 0.0118 (16) |
C5' | 0.044 (2) | 0.051 (2) | 0.074 (3) | 0.0041 (17) | 0.0115 (19) | 0.012 (2) |
C6' | 0.069 (3) | 0.074 (3) | 0.081 (3) | 0.014 (2) | 0.035 (2) | 0.013 (2) |
C7' | 0.078 (3) | 0.082 (3) | 0.049 (2) | 0.020 (2) | 0.018 (2) | 0.003 (2) |
C8' | 0.054 (2) | 0.064 (3) | 0.058 (2) | 0.0115 (19) | 0.0110 (19) | 0.004 (2) |
C17B | 0.078 (3) | 0.059 (2) | 0.046 (2) | 0.005 (2) | 0.016 (2) | 0.0140 (19) |
C21B | 0.059 (2) | 0.051 (2) | 0.042 (2) | −0.0003 (17) | 0.0014 (17) | 0.0083 (17) |
C12' | 0.051 (2) | 0.056 (2) | 0.049 (2) | 0.0030 (18) | 0.0020 (17) | 0.0134 (18) |
C14' | 0.056 (2) | 0.050 (2) | 0.045 (2) | 0.0013 (17) | 0.0047 (17) | 0.0041 (17) |
C15' | 0.067 (2) | 0.075 (3) | 0.051 (2) | 0.016 (2) | 0.008 (2) | −0.001 (2) |
C16' | 0.076 (3) | 0.097 (4) | 0.049 (3) | 0.007 (3) | 0.020 (2) | −0.002 (2) |
C17' | 0.090 (3) | 0.083 (3) | 0.047 (2) | −0.002 (3) | 0.016 (2) | 0.012 (2) |
C18' | 0.113 (4) | 0.094 (4) | 0.068 (3) | 0.034 (3) | 0.017 (3) | 0.041 (3) |
C19' | 0.109 (4) | 0.131 (5) | 0.097 (4) | 0.062 (4) | 0.026 (3) | 0.058 (4) |
C20' | 0.082 (3) | 0.114 (4) | 0.089 (4) | 0.038 (3) | 0.027 (3) | 0.046 (3) |
C21' | 0.058 (2) | 0.082 (3) | 0.067 (3) | 0.015 (2) | 0.019 (2) | 0.030 (2) |
C13' | 0.103 (3) | 0.050 (3) | 0.070 (3) | −0.014 (2) | 0.002 (3) | 0.010 (2) |
O2—S1 | 1.426 (3) | S1'—O1' | 1.426 (3) |
S1—O1 | 1.427 (3) | S1'—O2' | 1.428 (3) |
S1—N2 | 1.620 (3) | S1'—N2' | 1.618 (3) |
S1—C8A | 1.765 (3) | S1'—C8B | 1.755 (3) |
N2—C3 | 1.478 (5) | N2'—C3' | 1.455 (6) |
N2—H2 | 0.9600 | N2'—H2' | 0.9477 |
N11—C4 | 1.513 (4) | N11'—C12' | 1.511 (4) |
N11—C12 | 1.551 (4) | N11'—C4' | 1.529 (4) |
N11—H11A | 0.9000 | N11'—H11C | 0.9000 |
N11—H11B | 0.9000 | N11'—H11D | 0.9000 |
C3—C4 | 1.521 (4) | C3'—C4' | 1.513 (5) |
C3—H3A | 0.9700 | C3'—H3C | 0.9700 |
C3—H3B | 0.9700 | C3'—H3D | 0.9700 |
C4—C4A | 1.523 (4) | C4'—C4B | 1.505 (5) |
C4—H4 | 0.9800 | C4'—H4' | 0.9800 |
C4A—C8A | 1.387 (4) | C4B—C8B | 1.392 (5) |
C4A—C5 | 1.388 (4) | C4B—C5' | 1.393 (5) |
C5—C6 | 1.375 (5) | C8B—C8' | 1.388 (5) |
C5—H5 | 0.9300 | C5'—C6' | 1.379 (6) |
C6—C7 | 1.375 (6) | C5'—H5' | 0.9300 |
C6—H6 | 0.9300 | C6'—C7' | 1.380 (6) |
C7—C8 | 1.385 (6) | C6'—H6' | 0.9300 |
C7—H7 | 0.9300 | C7'—C8' | 1.380 (5) |
C8—C8A | 1.399 (5) | C7'—H7' | 0.9300 |
C8—H8 | 0.9300 | C8'—H8' | 0.9300 |
C12—C14 | 1.507 (5) | C17B—C18' | 1.400 (7) |
C12—C13 | 1.514 (5) | C17B—C17' | 1.403 (6) |
C12—H12 | 0.9800 | C17B—C21B | 1.437 (5) |
C14—C15 | 1.376 (5) | C21B—C14' | 1.415 (5) |
C14—C21A | 1.425 (5) | C21B—C21' | 1.425 (5) |
C15—C16 | 1.389 (6) | C12'—C13' | 1.516 (6) |
C15—H15 | 0.9300 | C12'—C14' | 1.531 (5) |
C16—C17 | 1.340 (7) | C12'—H12' | 0.9800 |
C16—H16 | 0.9300 | C14'—C15' | 1.375 (5) |
C17—C17A | 1.414 (7) | C15'—C16' | 1.393 (7) |
C17—H17 | 0.9300 | C15'—H15' | 0.9300 |
C18—C19 | 1.346 (10) | C16'—C17' | 1.371 (7) |
C18—C17A | 1.411 (7) | C16'—H16' | 0.9300 |
C18—H18 | 0.9300 | C17'—H17' | 0.9300 |
C19—C20 | 1.415 (10) | C18'—C19' | 1.339 (7) |
C19—H19 | 0.9300 | C18'—H18' | 0.9300 |
C20—C21 | 1.379 (6) | C19'—C20' | 1.390 (7) |
C20—H20 | 0.9300 | C19'—H19' | 0.9300 |
C21—C21A | 1.419 (6) | C20'—C21' | 1.349 (6) |
C21—H21 | 0.9300 | C20'—H20' | 0.9300 |
C13—H13A | 0.9600 | C21'—H21' | 0.9300 |
C13—H13B | 0.9600 | C13'—H13D | 0.9600 |
C13—H13C | 0.9600 | C13'—H13E | 0.9600 |
C17A—C21A | 1.422 (6) | C13'—H13F | 0.9600 |
O2—S1—O1 | 118.82 (19) | O1'—S1'—O2' | 118.33 (17) |
O2—S1—N2 | 108.80 (18) | O1'—S1'—N2' | 107.53 (19) |
O1—S1—N2 | 107.58 (18) | O2'—S1'—N2' | 108.52 (18) |
O2—S1—C8A | 106.63 (15) | O1'—S1'—C8B | 110.57 (17) |
O1—S1—C8A | 110.18 (17) | O2'—S1'—C8B | 106.75 (17) |
N2—S1—C8A | 103.84 (15) | N2'—S1'—C8B | 104.25 (16) |
C3—N2—S1 | 113.3 (2) | C3'—N2'—S1' | 115.6 (3) |
C3—N2—H2 | 111.3 | C3'—N2'—H2' | 121.8 |
S1—N2—H2 | 111.9 | S1'—N2'—H2' | 102.9 |
C4—N11—C12 | 118.7 (2) | C12'—N11'—C4' | 115.3 (3) |
C4—N11—H11A | 107.6 | C12'—N11'—H11C | 108.4 |
C12—N11—H11A | 107.6 | C4'—N11'—H11C | 108.4 |
C4—N11—H11B | 107.6 | C12'—N11'—H11D | 108.4 |
C12—N11—H11B | 107.6 | C4'—N11'—H11D | 108.4 |
H11A—N11—H11B | 107.1 | H11C—N11'—H11D | 107.5 |
N2—C3—C4 | 113.7 (3) | N2'—C3'—C4' | 112.3 (3) |
N2—C3—H3A | 108.8 | N2'—C3'—H3C | 109.1 |
C4—C3—H3A | 108.8 | C4'—C3'—H3C | 109.1 |
N2—C3—H3B | 108.8 | N2'—C3'—H3D | 109.1 |
C4—C3—H3B | 108.8 | C4'—C3'—H3D | 109.1 |
H3A—C3—H3B | 107.7 | H3C—C3'—H3D | 107.9 |
N11—C4—C3 | 111.8 (3) | C4B—C4'—C3' | 112.9 (3) |
N11—C4—C4A | 110.2 (2) | C4B—C4'—N11' | 111.1 (3) |
C3—C4—C4A | 113.0 (3) | C3'—C4'—N11' | 109.8 (3) |
N11—C4—H4 | 107.2 | C4B—C4'—H4' | 107.6 |
C3—C4—H4 | 107.2 | C3'—C4'—H4' | 107.6 |
C4A—C4—H4 | 107.2 | N11'—C4'—H4' | 107.6 |
C8A—C4A—C5 | 117.6 (3) | C8B—C4B—C5' | 117.8 (3) |
C8A—C4A—C4 | 123.2 (3) | C8B—C4B—C4' | 122.0 (3) |
C5—C4A—C4 | 119.0 (3) | C5'—C4B—C4' | 120.2 (3) |
C6—C5—C4A | 121.5 (3) | C8'—C8B—C4B | 121.1 (3) |
C6—C5—H5 | 119.3 | C8'—C8B—S1' | 116.2 (3) |
C4A—C5—H5 | 119.3 | C4B—C8B—S1' | 122.6 (3) |
C5—C6—C7 | 120.4 (3) | C6'—C5'—C4B | 121.3 (3) |
C5—C6—H6 | 119.8 | C6'—C5'—H5' | 119.3 |
C7—C6—H6 | 119.8 | C4B—C5'—H5' | 119.3 |
C6—C7—C8 | 120.1 (3) | C5'—C6'—C7' | 119.9 (4) |
C6—C7—H7 | 119.9 | C5'—C6'—H6' | 120.0 |
C8—C7—H7 | 119.9 | C7'—C6'—H6' | 120.0 |
C7—C8—C8A | 118.8 (3) | C8'—C7'—C6' | 120.0 (4) |
C7—C8—H8 | 120.6 | C8'—C7'—H7' | 120.0 |
C8A—C8—H8 | 120.6 | C6'—C7'—H7' | 120.0 |
C14—C12—C13 | 115.1 (3) | C7'—C8'—C8B | 119.8 (4) |
C14—C12—N11 | 111.2 (3) | C7'—C8'—H8' | 120.1 |
C13—C12—N11 | 109.9 (3) | C8B—C8'—H8' | 120.1 |
C14—C12—H12 | 106.7 | C18'—C17B—C17' | 121.8 (4) |
C13—C12—H12 | 106.7 | C18'—C17B—C21B | 119.5 (4) |
N11—C12—H12 | 106.7 | C17'—C17B—C21B | 118.8 (4) |
C15—C14—C21A | 119.4 (4) | C14'—C21B—C21' | 124.3 (4) |
C15—C14—C12 | 120.9 (3) | C14'—C21B—C17B | 119.2 (4) |
C21A—C14—C12 | 119.7 (3) | C21'—C21B—C17B | 116.5 (4) |
C14—C15—C16 | 121.6 (4) | N11'—C12'—C13' | 107.8 (3) |
C14—C15—H15 | 119.2 | N11'—C12'—C14' | 108.3 (3) |
C16—C15—H15 | 119.2 | C13'—C12'—C14' | 115.1 (3) |
C17—C16—C15 | 120.4 (4) | N11'—C12'—H12' | 108.5 |
C17—C16—H16 | 119.8 | C13'—C12'—H12' | 108.5 |
C15—C16—H16 | 119.8 | C14'—C12'—H12' | 108.5 |
C16—C17—C17A | 121.0 (4) | C15'—C14'—C21B | 119.0 (4) |
C16—C17—H17 | 119.5 | C15'—C14'—C12' | 119.8 (4) |
C17A—C17—H17 | 119.5 | C21B—C14'—C12' | 121.1 (3) |
C19—C18—C17A | 120.6 (7) | C14'—C15'—C16' | 122.3 (4) |
C19—C18—H18 | 119.7 | C14'—C15'—H15' | 118.8 |
C17A—C18—H18 | 119.7 | C16'—C15'—H15' | 118.8 |
C18—C19—C20 | 121.9 (6) | C17'—C16'—C15' | 119.4 (4) |
C18—C19—H19 | 119.0 | C17'—C16'—H16' | 120.3 |
C20—C19—H19 | 119.0 | C15'—C16'—H16' | 120.3 |
C21—C20—C19 | 119.0 (6) | C16'—C17'—C17B | 121.2 (4) |
C21—C20—H20 | 120.5 | C16'—C17'—H17' | 119.4 |
C19—C20—H20 | 120.5 | C17B—C17'—H17' | 119.4 |
C20—C21—C21A | 120.4 (5) | C19'—C18'—C17B | 121.4 (5) |
C20—C21—H21 | 119.8 | C19'—C18'—H18' | 119.3 |
C21A—C21—H21 | 119.8 | C17B—C18'—H18' | 119.3 |
C12—C13—H13A | 109.5 | C18'—C19'—C20' | 120.2 (5) |
C12—C13—H13B | 109.5 | C18'—C19'—H19' | 119.9 |
H13A—C13—H13B | 109.5 | C20'—C19'—H19' | 119.9 |
C12—C13—H13C | 109.5 | C21'—C20'—C19' | 121.2 (5) |
H13A—C13—H13C | 109.5 | C21'—C20'—H20' | 119.4 |
H13B—C13—H13C | 109.5 | C19'—C20'—H20' | 119.4 |
C4A—C8A—C8 | 121.6 (3) | C20'—C21'—C21B | 121.2 (4) |
C4A—C8A—S1 | 122.1 (2) | C20'—C21'—H21' | 119.4 |
C8—C8A—S1 | 116.2 (3) | C21B—C21'—H21' | 119.4 |
C18—C17A—C17 | 121.8 (6) | C12'—C13'—H13D | 109.5 |
C18—C17A—C21A | 118.8 (6) | C12'—C13'—H13E | 109.5 |
C17—C17A—C21A | 119.4 (4) | H13D—C13'—H13E | 109.5 |
C21—C21A—C17A | 119.3 (4) | C12'—C13'—H13F | 109.5 |
C21—C21A—C14 | 122.6 (4) | H13D—C13'—H13F | 109.5 |
C17A—C21A—C14 | 118.1 (4) | H13E—C13'—H13F | 109.5 |
O2—S1—N2—C3 | −67.2 (3) | O1'—S1'—N2'—C3' | 155.8 (3) |
O1—S1—N2—C3 | 162.9 (2) | O2'—S1'—N2'—C3' | −75.1 (3) |
C8A—S1—N2—C3 | 46.1 (3) | C8B—S1'—N2'—C3' | 38.4 (3) |
S1—N2—C3—C4 | −67.8 (3) | S1'—N2'—C3'—C4' | −65.9 (4) |
C12—N11—C4—C3 | −79.2 (3) | N2'—C3'—C4'—C4B | 54.7 (4) |
C12—N11—C4—C4A | 154.3 (2) | N2'—C3'—C4'—N11' | −70.0 (4) |
N2—C3—C4—N11 | −76.4 (4) | C12'—N11'—C4'—C4B | 121.0 (3) |
N2—C3—C4—C4A | 48.5 (4) | C12'—N11'—C4'—C3' | −113.3 (3) |
N11—C4—C4A—C8A | 110.9 (3) | C3'—C4'—C4B—C8B | −21.6 (5) |
C3—C4—C4A—C8A | −14.9 (4) | N11'—C4'—C4B—C8B | 102.3 (4) |
N11—C4—C4A—C5 | −73.3 (4) | C3'—C4'—C4B—C5' | 156.5 (3) |
C3—C4—C4A—C5 | 160.8 (3) | N11'—C4'—C4B—C5' | −79.6 (4) |
C8A—C4A—C5—C6 | −0.7 (5) | C5'—C4B—C8B—C8' | −0.6 (5) |
C4—C4A—C5—C6 | −176.6 (3) | C4'—C4B—C8B—C8' | 177.5 (3) |
C4A—C5—C6—C7 | 1.1 (6) | C5'—C4B—C8B—S1' | −179.0 (3) |
C5—C6—C7—C8 | −1.5 (6) | C4'—C4B—C8B—S1' | −1.0 (5) |
C6—C7—C8—C8A | 1.6 (6) | O1'—S1'—C8B—C8' | 60.1 (3) |
C4—N11—C12—C14 | −26.9 (4) | O2'—S1'—C8B—C8' | −69.9 (3) |
C4—N11—C12—C13 | 101.7 (4) | N2'—S1'—C8B—C8' | 175.4 (3) |
C13—C12—C14—C15 | −19.0 (5) | O1'—S1'—C8B—C4B | −121.4 (3) |
N11—C12—C14—C15 | 106.8 (3) | O2'—S1'—C8B—C4B | 108.7 (3) |
C13—C12—C14—C21A | 160.0 (3) | N2'—S1'—C8B—C4B | −6.1 (3) |
N11—C12—C14—C21A | −74.2 (4) | C8B—C4B—C5'—C6' | 0.4 (6) |
C21A—C14—C15—C16 | 1.3 (5) | C4'—C4B—C5'—C6' | −177.8 (4) |
C12—C14—C15—C16 | −179.7 (3) | C4B—C5'—C6'—C7' | 0.2 (7) |
C14—C15—C16—C17 | 1.3 (6) | C5'—C6'—C7'—C8' | −0.5 (7) |
C15—C16—C17—C17A | −1.7 (6) | C6'—C7'—C8'—C8B | 0.3 (7) |
C17A—C18—C19—C20 | −1.1 (9) | C4B—C8B—C8'—C7' | 0.2 (6) |
C18—C19—C20—C21 | 2.0 (9) | S1'—C8B—C8'—C7' | 178.8 (3) |
C19—C20—C21—C21A | −0.9 (7) | C18'—C17B—C21B—C14' | 179.6 (4) |
C5—C4A—C8A—C8 | 0.7 (5) | C17'—C17B—C21B—C14' | 0.2 (5) |
C4—C4A—C8A—C8 | 176.5 (3) | C18'—C17B—C21B—C21' | 0.0 (6) |
C5—C4A—C8A—S1 | −175.7 (3) | C17'—C17B—C21B—C21' | −179.4 (4) |
C4—C4A—C8A—S1 | 0.1 (5) | C4'—N11'—C12'—C13' | −178.5 (3) |
C7—C8—C8A—C4A | −1.1 (5) | C4'—N11'—C12'—C14' | 56.3 (4) |
C7—C8—C8A—S1 | 175.5 (3) | C21'—C21B—C14'—C15' | 176.3 (4) |
O2—S1—C8A—C4A | 100.4 (3) | C17B—C21B—C14'—C15' | −3.3 (5) |
O1—S1—C8A—C4A | −129.4 (3) | C21'—C21B—C14'—C12' | −7.2 (5) |
N2—S1—C8A—C4A | −14.4 (3) | C17B—C21B—C14'—C12' | 173.3 (3) |
O2—S1—C8A—C8 | −76.2 (3) | N11'—C12'—C14'—C15' | 63.8 (4) |
O1—S1—C8A—C8 | 54.0 (3) | C13'—C12'—C14'—C15' | −56.9 (5) |
N2—S1—C8A—C8 | 169.0 (3) | N11'—C12'—C14'—C21B | −112.7 (4) |
C19—C18—C17A—C17 | 177.8 (5) | C13'—C12'—C14'—C21B | 126.6 (4) |
C19—C18—C17A—C21A | −0.9 (7) | C21B—C14'—C15'—C16' | 3.9 (6) |
C16—C17—C17A—C18 | −179.1 (4) | C12'—C14'—C15'—C16' | −172.7 (4) |
C16—C17—C17A—C21A | −0.4 (6) | C14'—C15'—C16'—C17' | −1.3 (6) |
C20—C21—C21A—C17A | −1.0 (5) | C15'—C16'—C17'—C17B | −2.0 (7) |
C20—C21—C21A—C14 | 179.3 (4) | C18'—C17B—C17'—C16' | −176.9 (5) |
C18—C17A—C21A—C21 | 1.9 (5) | C21B—C17B—C17'—C16' | 2.5 (6) |
C17—C17A—C21A—C21 | −176.8 (4) | C17'—C17B—C18'—C19' | −179.4 (5) |
C18—C17A—C21A—C14 | −178.4 (4) | C21B—C17B—C18'—C19' | 1.2 (8) |
C17—C17A—C21A—C14 | 2.9 (5) | C17B—C18'—C19'—C20' | −2.1 (9) |
C15—C14—C21A—C21 | 176.4 (3) | C18'—C19'—C20'—C21' | 1.6 (9) |
C12—C14—C21A—C21 | −2.6 (5) | C19'—C20'—C21'—C21B | −0.4 (8) |
C15—C14—C21A—C17A | −3.3 (5) | C14'—C21B—C21'—C20' | −179.9 (4) |
C12—C14—C21A—C17A | 177.6 (3) | C17B—C21B—C21'—C20' | −0.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1 | 0.96 | 2.22 | 3.172 (3) | 173 |
N11—H11B···Cl1 | 0.90 | 2.30 | 3.195 (3) | 176 |
N11—H11A···Cl1′ | 0.90 | 2.22 | 3.049 (2) | 153 |
N2′—H2′···Cl1 | 0.95 | 2.39 | 3.154 (3) | 138 |
N11′—H11D···Cl1′ | 0.90 | 2.20 | 3.067 (3) | 163 |
N11′—H11C···Cl1 | 0.90 | 2.34 | 3.229 (3) | 170 |
C4—H4···O2′i | 0.98 | 2.36 | 3.114 (4) | 133 |
C19—H19···O1ii | 0.93 | 2.60 | 3.465 (7) | 155 |
C6′—H6′···O1′iii | 0.93 | 2.47 | 3.234 (5) | 139 |
Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) x−1, y, z. |
C26H25N2O2S+·Cl− | F(000) = 976 |
Mr = 464.99 | Dx = 1.305 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2yb | Cell parameters from 4252 reflections |
a = 15.295 (4) Å | θ = 1.0–25.0° |
b = 7.764 (3) Å | µ = 0.28 mm−1 |
c = 20.264 (6) Å | T = 293 K |
β = 100.48 (2)° | Prism, colourless |
V = 2366.2 (13) Å3 | 0.50 × 0.22 × 0.13 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 8155 independent reflections |
Radiation source: fine-focus sealed tube | 5732 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
phi and ω scans | θmax = 25.1°, θmin = 1.0° |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | h = −18→18 |
Tmin = 0.89, Tmax = 0.97 | k = −8→9 |
14090 measured reflections | l = −24→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0532P)2 + 0.2294P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
8155 reflections | Δρmax = 0.18 e Å−3 |
579 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3619 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.11 (6) |
C26H25N2O2S+·Cl− | V = 2366.2 (13) Å3 |
Mr = 464.99 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 15.295 (4) Å | µ = 0.28 mm−1 |
b = 7.764 (3) Å | T = 293 K |
c = 20.264 (6) Å | 0.50 × 0.22 × 0.13 mm |
β = 100.48 (2)° |
Nonius KappaCCD diffractometer | 8155 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 5732 reflections with I > 2σ(I) |
Tmin = 0.89, Tmax = 0.97 | Rint = 0.035 |
14090 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.118 | Δρmax = 0.18 e Å−3 |
S = 1.01 | Δρmin = −0.26 e Å−3 |
8155 reflections | Absolute structure: Flack (1983), 3619 Friedel pairs |
579 parameters | Absolute structure parameter: −0.11 (6) |
1 restraint |
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 except three low resolution reflections truncated by the beamstop. 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. Checkcif output 340_ALERT_3_C Low Bond Precision on C—C Bonds (x 1000) Ang ··· 6 234_ALERT_4_C Large Hirshfeld Difference C22 – C23.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C24 – C25.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference N15' – C16'.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C8' – C9'.. 0.12 A ng. 234_ALERT_4_C Large Hirshfeld Difference C9' – C10'.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C11' – C11B.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C19' – C20'.. 0.13 A ng. 791_ALERT_4_G The Model has Chirality at C3 R 791_ALERT_4_G The Model has Chirality at C3' R 791_ALERT_4_G The Model has Chirality at C16 R 791_ALERT_4_G The Model has Chirality at C16' R |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.48525 (7) | 0.85993 (11) | 0.06579 (4) | 0.0578 (3) | |
S1 | 0.79490 (6) | 0.34067 (11) | 0.03221 (5) | 0.0548 (3) | |
O2 | 0.78249 (19) | 0.2739 (4) | −0.03463 (14) | 0.0762 (9) | |
O1 | 0.85402 (18) | 0.2539 (3) | 0.08520 (15) | 0.0668 (8) | |
N2 | 0.69581 (17) | 0.3491 (4) | 0.05154 (14) | 0.0516 (8) | |
H2 | 0.6486 | 0.3519 | 0.0116 | 0.062* | |
N15 | 0.50914 (16) | 0.4545 (3) | 0.08190 (13) | 0.0410 (7) | |
H15A | 0.5150 | 0.4287 | 0.0396 | 0.049* | |
H15B | 0.5013 | 0.5691 | 0.0841 | 0.049* | |
C3 | 0.6767 (2) | 0.4670 (4) | 0.10442 (15) | 0.0403 (8) | |
H3 | 0.6652 | 0.5818 | 0.0846 | 0.048* | |
C4 | 0.7534 (2) | 0.3996 (5) | 0.22363 (17) | 0.0531 (9) | |
H4 | 0.7049 | 0.3313 | 0.2283 | 0.064* | |
C5 | 0.8232 (2) | 0.4194 (5) | 0.27756 (18) | 0.0595 (10) | |
H5 | 0.8214 | 0.3649 | 0.3182 | 0.071* | |
C6 | 0.8950 (3) | 0.5200 (5) | 0.2705 (2) | 0.0584 (10) | |
H6 | 0.9415 | 0.5349 | 0.3067 | 0.070* | |
C7 | 0.8983 (2) | 0.5980 (5) | 0.21059 (19) | 0.0547 (10) | |
H7 | 0.9474 | 0.6651 | 0.2064 | 0.066* | |
C8 | 0.8746 (2) | 0.8217 (4) | 0.08621 (19) | 0.0529 (9) | |
H8 | 0.8807 | 0.8930 | 0.1236 | 0.063* | |
C9 | 0.8977 (2) | 0.8839 (5) | 0.0278 (2) | 0.0610 (11) | |
H9 | 0.9208 | 0.9946 | 0.0269 | 0.073* | |
C10 | 0.8869 (3) | 0.7831 (5) | −0.0290 (2) | 0.0659 (11) | |
H10 | 0.9032 | 0.8250 | −0.0680 | 0.079* | |
C11 | 0.8517 (3) | 0.6194 (5) | −0.0278 (2) | 0.0594 (10) | |
H11 | 0.8421 | 0.5523 | −0.0665 | 0.071* | |
C14 | 0.5925 (2) | 0.4066 (5) | 0.12817 (16) | 0.0477 (9) | |
H14A | 0.5947 | 0.2823 | 0.1331 | 0.057* | |
H14B | 0.5915 | 0.4558 | 0.1720 | 0.057* | |
C16 | 0.4275 (2) | 0.3651 (4) | 0.09725 (16) | 0.0424 (8) | |
H16 | 0.4348 | 0.2410 | 0.0912 | 0.051* | |
C17 | 0.3474 (2) | 0.4248 (6) | 0.04628 (19) | 0.0658 (11) | |
H17A | 0.2959 | 0.3603 | 0.0522 | 0.099* | |
H17B | 0.3587 | 0.4066 | 0.0017 | 0.099* | |
H17C | 0.3373 | 0.5451 | 0.0528 | 0.099* | |
C18 | 0.4157 (2) | 0.3960 (4) | 0.16918 (17) | 0.0428 (8) | |
C19 | 0.4369 (3) | 0.5496 (5) | 0.2007 (2) | 0.0554 (10) | |
H19 | 0.4580 | 0.6390 | 0.1773 | 0.066* | |
C20 | 0.4278 (3) | 0.5760 (5) | 0.2678 (2) | 0.0658 (12) | |
H20 | 0.4444 | 0.6806 | 0.2887 | 0.079* | |
C21 | 0.3948 (3) | 0.4486 (6) | 0.3017 (2) | 0.0667 (12) | |
H21 | 0.3894 | 0.4671 | 0.3462 | 0.080* | |
C22 | 0.3333 (3) | 0.1549 (6) | 0.3068 (2) | 0.0695 (12) | |
H22 | 0.3261 | 0.1722 | 0.3510 | 0.083* | |
C23 | 0.3101 (3) | 0.0033 (6) | 0.2767 (2) | 0.0740 (13) | |
H23 | 0.2880 | −0.0838 | 0.3006 | 0.089* | |
C24 | 0.3183 (3) | −0.0260 (5) | 0.2103 (2) | 0.0675 (12) | |
H24 | 0.3011 | −0.1312 | 0.1902 | 0.081* | |
C25 | 0.3516 (2) | 0.0991 (4) | 0.1749 (2) | 0.0521 (9) | |
H25 | 0.3566 | 0.0780 | 0.1306 | 0.063* | |
Cl1' | 0.99298 (7) | 0.90502 (13) | 0.56547 (4) | 0.0629 (3) | |
S1' | 0.70754 (7) | 0.89593 (15) | 0.48265 (6) | 0.0724 (4) | |
O1' | 0.6477 (2) | 0.7933 (4) | 0.43710 (19) | 0.0915 (11) | |
O2' | 0.7273 (2) | 0.8506 (5) | 0.55231 (16) | 0.1090 (13) | |
C3' | 0.8155 (2) | 1.0053 (4) | 0.39928 (16) | 0.0435 (8) | |
H3' | 0.8252 | 1.1255 | 0.4136 | 0.052* | |
C3B | 0.7343 (2) | 0.9975 (4) | 0.34289 (18) | 0.0463 (9) | |
N2' | 0.80313 (19) | 0.9011 (4) | 0.45786 (15) | 0.0615 (9) | |
H2' | 0.8393 | 0.9070 | 0.4922 | 0.074* | |
C4' | 0.7342 (2) | 0.9022 (5) | 0.28492 (19) | 0.0620 (10) | |
H4' | 0.7839 | 0.8365 | 0.2810 | 0.074* | |
C4A | 0.7553 (2) | 0.4809 (4) | 0.16275 (17) | 0.0408 (8) | |
C5' | 0.6621 (3) | 0.9026 (6) | 0.2328 (2) | 0.0727 (12) | |
H5' | 0.6636 | 0.8391 | 0.1942 | 0.087* | |
C6' | 0.5879 (3) | 0.9976 (6) | 0.2385 (2) | 0.0710 (12) | |
H6' | 0.5393 | 0.9991 | 0.2035 | 0.085* | |
C7' | 0.5857 (3) | 1.0894 (5) | 0.2954 (2) | 0.0655 (11) | |
H7' | 0.5350 | 1.1527 | 0.2987 | 0.079* | |
C7A | 0.8291 (2) | 0.5789 (4) | 0.15508 (17) | 0.0431 (8) | |
C7B | 0.6578 (2) | 1.0910 (4) | 0.34908 (18) | 0.0482 (9) | |
C8' | 0.6091 (3) | 1.3485 (5) | 0.4081 (2) | 0.0678 (11) | |
H8' | 0.5971 | 1.4053 | 0.3670 | 0.081* | |
C8A | 0.8423 (2) | 0.6550 (4) | 0.09046 (17) | 0.0419 (8) | |
C8B | 0.6471 (2) | 1.1841 (5) | 0.4121 (2) | 0.0507 (10) | |
C9' | 0.5891 (3) | 1.4273 (6) | 0.4651 (3) | 0.0788 (14) | |
H9' | 0.5629 | 1.5358 | 0.4617 | 0.095* | |
C10' | 0.6075 (3) | 1.3470 (7) | 0.5261 (3) | 0.0875 (15) | |
H10' | 0.5923 | 1.3994 | 0.5637 | 0.105* | |
C11' | 0.6486 (3) | 1.1884 (7) | 0.5318 (3) | 0.0795 (14) | |
H11' | 0.6643 | 1.1358 | 0.5735 | 0.095* | |
C11A | 0.8309 (2) | 0.5560 (4) | 0.03134 (18) | 0.0450 (9) | |
C11B | 0.6663 (2) | 1.1087 (5) | 0.4747 (2) | 0.0570 (10) | |
C14' | 0.8986 (2) | 0.9409 (5) | 0.37463 (17) | 0.0496 (9) | |
H14C | 0.8977 | 0.8160 | 0.3736 | 0.059* | |
H14D | 0.8968 | 0.9811 | 0.3291 | 0.059* | |
N15' | 0.98325 (17) | 0.9991 (4) | 0.41705 (13) | 0.0445 (7) | |
H15C | 0.9816 | 0.9755 | 0.4603 | 0.053* | |
H15D | 0.9880 | 1.1140 | 0.4131 | 0.053* | |
C16' | 1.0644 (2) | 0.9145 (5) | 0.39831 (16) | 0.0453 (8) | |
H16' | 1.0611 | 0.7905 | 0.4067 | 0.054* | |
C17' | 1.1470 (2) | 0.9853 (6) | 0.4442 (2) | 0.0733 (13) | |
H17D | 1.1988 | 0.9271 | 0.4350 | 0.110* | |
H17E | 1.1419 | 0.9670 | 0.4902 | 0.110* | |
H17F | 1.1521 | 1.1065 | 0.4361 | 0.110* | |
C18' | 1.0678 (2) | 0.9404 (4) | 0.32454 (18) | 0.0472 (9) | |
C19' | 1.0428 (3) | 1.0933 (5) | 0.2931 (2) | 0.0587 (10) | |
H19' | 1.0253 | 1.1836 | 0.3178 | 0.070* | |
C20' | 1.0427 (3) | 1.1174 (6) | 0.2249 (2) | 0.0734 (12) | |
H20' | 1.0244 | 1.2220 | 0.2047 | 0.088* | |
C21' | 1.0692 (3) | 0.9893 (7) | 0.1884 (2) | 0.0725 (13) | |
H21' | 1.0666 | 1.0052 | 0.1426 | 0.087* | |
C21A | 0.3686 (2) | 0.2889 (5) | 0.27170 (19) | 0.0529 (10) | |
C21B | 1.1011 (2) | 0.8306 (6) | 0.2182 (2) | 0.0598 (11) | |
C22' | 1.1327 (3) | 0.6971 (8) | 0.1814 (3) | 0.0801 (15) | |
H22' | 1.1324 | 0.7121 | 0.1358 | 0.096* | |
C23' | 1.1637 (3) | 0.5460 (7) | 0.2116 (3) | 0.0839 (15) | |
H23' | 1.1854 | 0.4603 | 0.1869 | 0.101* | |
C24' | 1.1628 (3) | 0.5206 (6) | 0.2794 (3) | 0.0738 (13) | |
H24' | 1.1835 | 0.4170 | 0.2995 | 0.089* | |
C25' | 1.1322 (2) | 0.6454 (5) | 0.3171 (2) | 0.0577 (10) | |
H25' | 1.1322 | 0.6256 | 0.3623 | 0.069* | |
C25A | 0.3784 (2) | 0.2594 (4) | 0.20383 (18) | 0.0425 (8) | |
C25B | 1.1003 (2) | 0.8048 (5) | 0.28783 (18) | 0.0502 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0746 (7) | 0.0584 (6) | 0.0395 (5) | 0.0002 (5) | 0.0085 (5) | 0.0039 (4) |
S1 | 0.0539 (6) | 0.0529 (6) | 0.0615 (7) | −0.0053 (4) | 0.0207 (5) | −0.0168 (5) |
O2 | 0.085 (2) | 0.0836 (19) | 0.067 (2) | −0.0207 (15) | 0.0330 (17) | −0.0386 (16) |
O1 | 0.0636 (18) | 0.0510 (15) | 0.086 (2) | 0.0111 (13) | 0.0136 (16) | −0.0015 (14) |
N2 | 0.0386 (16) | 0.070 (2) | 0.0468 (18) | −0.0110 (14) | 0.0083 (13) | −0.0178 (15) |
N15 | 0.0407 (16) | 0.0490 (17) | 0.0330 (16) | −0.0036 (12) | 0.0057 (13) | 0.0013 (12) |
C3 | 0.043 (2) | 0.0456 (19) | 0.0312 (19) | −0.0042 (14) | 0.0041 (16) | −0.0005 (14) |
C4 | 0.045 (2) | 0.062 (2) | 0.049 (2) | −0.0104 (17) | 0.0016 (18) | 0.0119 (19) |
C5 | 0.059 (3) | 0.072 (3) | 0.042 (2) | −0.004 (2) | −0.0040 (19) | 0.011 (2) |
C6 | 0.053 (2) | 0.069 (2) | 0.045 (3) | −0.0024 (19) | −0.0126 (19) | 0.0016 (19) |
C7 | 0.038 (2) | 0.070 (2) | 0.053 (3) | −0.0074 (17) | −0.0001 (19) | −0.008 (2) |
C8 | 0.049 (2) | 0.049 (2) | 0.061 (3) | −0.0025 (17) | 0.0104 (19) | −0.0040 (18) |
C9 | 0.057 (2) | 0.051 (2) | 0.079 (3) | 0.0002 (18) | 0.025 (2) | 0.015 (2) |
C10 | 0.065 (3) | 0.074 (3) | 0.065 (3) | 0.005 (2) | 0.028 (2) | 0.016 (2) |
C11 | 0.059 (3) | 0.071 (3) | 0.054 (3) | 0.004 (2) | 0.024 (2) | −0.006 (2) |
C14 | 0.0355 (19) | 0.068 (2) | 0.039 (2) | −0.0024 (16) | 0.0049 (16) | 0.0071 (18) |
C16 | 0.0351 (18) | 0.050 (2) | 0.042 (2) | −0.0034 (15) | 0.0061 (15) | 0.0037 (16) |
C17 | 0.042 (2) | 0.091 (3) | 0.060 (3) | −0.005 (2) | −0.0001 (19) | 0.010 (2) |
C18 | 0.0348 (18) | 0.050 (2) | 0.045 (2) | 0.0049 (15) | 0.0116 (15) | 0.0042 (16) |
C19 | 0.065 (3) | 0.047 (2) | 0.057 (3) | 0.0034 (17) | 0.018 (2) | −0.0038 (18) |
C20 | 0.079 (3) | 0.060 (3) | 0.063 (3) | 0.010 (2) | 0.027 (2) | −0.011 (2) |
C21 | 0.071 (3) | 0.085 (3) | 0.047 (3) | 0.021 (2) | 0.021 (2) | −0.001 (2) |
C22 | 0.056 (3) | 0.095 (3) | 0.063 (3) | 0.017 (2) | 0.025 (2) | 0.030 (3) |
C23 | 0.056 (3) | 0.083 (3) | 0.086 (4) | −0.004 (2) | 0.022 (3) | 0.033 (3) |
C24 | 0.056 (3) | 0.065 (3) | 0.081 (3) | −0.0052 (19) | 0.012 (2) | 0.013 (2) |
C25 | 0.046 (2) | 0.050 (2) | 0.062 (3) | −0.0014 (16) | 0.0140 (19) | 0.0070 (18) |
Cl1' | 0.0778 (7) | 0.0712 (8) | 0.0371 (5) | 0.0038 (5) | 0.0033 (5) | 0.0047 (5) |
S1' | 0.0594 (7) | 0.0818 (9) | 0.0820 (8) | 0.0098 (6) | 0.0289 (6) | 0.0368 (7) |
O1' | 0.071 (2) | 0.0602 (19) | 0.148 (3) | −0.0085 (15) | 0.031 (2) | 0.0243 (19) |
O2' | 0.101 (2) | 0.151 (3) | 0.087 (2) | 0.042 (2) | 0.049 (2) | 0.073 (2) |
C3' | 0.039 (2) | 0.055 (2) | 0.037 (2) | 0.0024 (15) | 0.0054 (16) | 0.0035 (16) |
C3B | 0.037 (2) | 0.051 (2) | 0.048 (2) | 0.0011 (15) | 0.0001 (17) | 0.0067 (17) |
N2' | 0.0470 (19) | 0.086 (2) | 0.052 (2) | 0.0112 (16) | 0.0126 (15) | 0.0251 (18) |
C4' | 0.046 (2) | 0.074 (3) | 0.061 (3) | 0.0043 (19) | −0.003 (2) | −0.012 (2) |
C4A | 0.0357 (19) | 0.0448 (18) | 0.040 (2) | −0.0005 (14) | 0.0025 (16) | −0.0016 (15) |
C5' | 0.053 (3) | 0.091 (3) | 0.065 (3) | 0.003 (2) | −0.012 (2) | −0.020 (2) |
C6' | 0.049 (3) | 0.092 (3) | 0.064 (3) | −0.003 (2) | −0.011 (2) | −0.005 (2) |
C7' | 0.043 (2) | 0.080 (3) | 0.069 (3) | 0.0111 (19) | −0.002 (2) | 0.007 (2) |
C7A | 0.040 (2) | 0.0455 (19) | 0.044 (2) | 0.0001 (15) | 0.0073 (17) | −0.0017 (15) |
C7B | 0.041 (2) | 0.052 (2) | 0.051 (2) | −0.0008 (16) | 0.0049 (18) | 0.0084 (17) |
C8' | 0.065 (3) | 0.060 (3) | 0.082 (3) | 0.004 (2) | 0.023 (2) | 0.004 (2) |
C8A | 0.036 (2) | 0.049 (2) | 0.041 (2) | −0.0005 (15) | 0.0095 (16) | 0.0014 (16) |
C8B | 0.036 (2) | 0.052 (2) | 0.065 (3) | −0.0011 (16) | 0.0114 (19) | 0.0051 (19) |
C9' | 0.066 (3) | 0.054 (3) | 0.123 (4) | −0.001 (2) | 0.034 (3) | −0.010 (3) |
C10' | 0.070 (3) | 0.098 (4) | 0.102 (4) | −0.018 (3) | 0.035 (3) | −0.035 (3) |
C11' | 0.062 (3) | 0.112 (4) | 0.069 (3) | −0.008 (3) | 0.023 (2) | 0.000 (3) |
C11A | 0.044 (2) | 0.046 (2) | 0.047 (2) | −0.0002 (15) | 0.0144 (17) | −0.0043 (16) |
C11B | 0.044 (2) | 0.075 (3) | 0.056 (3) | −0.0027 (18) | 0.018 (2) | 0.009 (2) |
C14' | 0.037 (2) | 0.073 (3) | 0.035 (2) | 0.0017 (16) | −0.0024 (16) | −0.0048 (17) |
N15' | 0.0412 (17) | 0.0571 (17) | 0.0342 (17) | −0.0001 (13) | 0.0045 (14) | 0.0025 (13) |
C16' | 0.0357 (19) | 0.059 (2) | 0.040 (2) | 0.0064 (16) | 0.0053 (16) | −0.0048 (17) |
C17' | 0.039 (2) | 0.112 (4) | 0.065 (3) | 0.005 (2) | −0.002 (2) | −0.016 (3) |
C18' | 0.037 (2) | 0.059 (2) | 0.047 (2) | −0.0070 (16) | 0.0101 (17) | −0.0053 (18) |
C19' | 0.066 (3) | 0.067 (3) | 0.047 (3) | −0.0065 (19) | 0.018 (2) | 0.0055 (19) |
C20' | 0.077 (3) | 0.082 (3) | 0.063 (3) | −0.015 (2) | 0.019 (3) | 0.011 (2) |
C21' | 0.070 (3) | 0.107 (4) | 0.041 (3) | −0.032 (3) | 0.012 (2) | 0.002 (3) |
C21A | 0.044 (2) | 0.067 (3) | 0.052 (3) | 0.0138 (18) | 0.0198 (19) | 0.0105 (19) |
C21B | 0.050 (2) | 0.086 (3) | 0.048 (3) | −0.024 (2) | 0.0206 (19) | −0.016 (2) |
C22' | 0.068 (3) | 0.113 (4) | 0.067 (3) | −0.036 (3) | 0.032 (3) | −0.036 (3) |
C23' | 0.071 (3) | 0.098 (4) | 0.089 (4) | −0.018 (3) | 0.033 (3) | −0.045 (3) |
C24' | 0.062 (3) | 0.074 (3) | 0.091 (4) | −0.005 (2) | 0.027 (3) | −0.022 (3) |
C25' | 0.049 (2) | 0.063 (3) | 0.064 (3) | −0.0062 (18) | 0.016 (2) | −0.012 (2) |
C25A | 0.035 (2) | 0.049 (2) | 0.045 (2) | 0.0111 (15) | 0.0110 (17) | 0.0097 (16) |
C25B | 0.038 (2) | 0.067 (2) | 0.047 (2) | −0.0185 (17) | 0.0131 (17) | −0.0122 (18) |
S1—O2 | 1.430 (3) | C3'—N2' | 1.477 (4) |
S1—O1 | 1.439 (3) | C3'—C3B | 1.529 (5) |
S1—N2 | 1.634 (3) | C3'—C14' | 1.531 (5) |
S1—C11A | 1.761 (3) | C3'—H3' | 0.9800 |
N2—C3 | 1.479 (4) | C3B—C4' | 1.388 (5) |
N2—H2 | 0.9820 | C3B—C7B | 1.402 (5) |
N15—C14 | 1.486 (4) | N2'—H2' | 0.8070 |
N15—C16 | 1.509 (4) | C4'—C5' | 1.381 (5) |
N15—H15A | 0.9000 | C4'—H4' | 0.9300 |
N15—H15B | 0.9000 | C4A—C7A | 1.394 (4) |
C3—C14 | 1.527 (4) | C5'—C6' | 1.375 (6) |
C3—C4A | 1.529 (4) | C5'—H5' | 0.9300 |
C3—H3 | 0.9800 | C6'—C7' | 1.360 (6) |
C4—C5 | 1.391 (5) | C6'—H6' | 0.9300 |
C4—C4A | 1.391 (5) | C7'—C7B | 1.402 (5) |
C4—H4 | 0.9300 | C7'—H7' | 0.9300 |
C5—C6 | 1.377 (5) | C7A—C8A | 1.483 (5) |
C5—H5 | 0.9300 | C7B—C8B | 1.502 (5) |
C6—C7 | 1.366 (5) | C8'—C9' | 1.390 (6) |
C6—H6 | 0.9300 | C8'—C8B | 1.399 (5) |
C7—C7A | 1.405 (5) | C8'—H8' | 0.9300 |
C7—H7 | 0.9300 | C8A—C11A | 1.407 (5) |
C8—C9 | 1.382 (5) | C8B—C11B | 1.380 (5) |
C8—C8A | 1.393 (5) | C9'—C10' | 1.368 (7) |
C8—H8 | 0.9300 | C9'—H9' | 0.9300 |
C9—C10 | 1.377 (6) | C10'—C11' | 1.378 (7) |
C9—H9 | 0.9300 | C10'—H10' | 0.9300 |
C10—C11 | 1.382 (6) | C11'—C11B | 1.381 (6) |
C10—H10 | 0.9300 | C11'—H11' | 0.9300 |
C11—C11A | 1.386 (5) | C14'—N15' | 1.488 (4) |
C11—H11 | 0.9300 | C14'—H14C | 0.9700 |
C14—H14A | 0.9700 | C14'—H14D | 0.9700 |
C14—H14B | 0.9700 | N15'—C16' | 1.513 (4) |
C16—C18 | 1.520 (4) | N15'—H15C | 0.9000 |
C16—C17 | 1.524 (5) | N15'—H15D | 0.9000 |
C16—H16 | 0.9800 | C16'—C18' | 1.519 (5) |
C17—H17A | 0.9600 | C16'—C17' | 1.528 (5) |
C17—H17B | 0.9600 | C16'—H16' | 0.9800 |
C17—H17C | 0.9600 | C17'—H17D | 0.9600 |
C18—C19 | 1.364 (5) | C17'—H17E | 0.9600 |
C18—C25A | 1.445 (4) | C17'—H17F | 0.9600 |
C19—C20 | 1.406 (5) | C18'—C19' | 1.369 (5) |
C19—H19 | 0.9300 | C18'—C25B | 1.429 (5) |
C20—C21 | 1.354 (6) | C19'—C20' | 1.394 (6) |
C20—H20 | 0.9300 | C19'—H19' | 0.9300 |
C21—C21A | 1.407 (6) | C20'—C21' | 1.345 (6) |
C21—H21 | 0.9300 | C20'—H20' | 0.9300 |
C22—C23 | 1.344 (6) | C21'—C21B | 1.419 (6) |
C22—C21A | 1.422 (5) | C21'—H21' | 0.9300 |
C22—H22 | 0.9300 | C21A—C25A | 1.429 (5) |
C23—C24 | 1.391 (6) | C21B—C22' | 1.413 (6) |
C23—H23 | 0.9300 | C21B—C25B | 1.428 (5) |
C24—C25 | 1.360 (5) | C22'—C23' | 1.368 (7) |
C24—H24 | 0.9300 | C22'—H22' | 0.9300 |
C25—C25A | 1.405 (5) | C23'—C24' | 1.389 (7) |
C25—H25 | 0.9300 | C23'—H23' | 0.9300 |
S1'—O1' | 1.421 (4) | C24'—C25' | 1.369 (5) |
S1'—O2' | 1.433 (3) | C24'—H24' | 0.9300 |
S1'—N2' | 1.631 (3) | C25'—C25B | 1.420 (5) |
S1'—C11B | 1.765 (4) | C25'—H25' | 0.9300 |
O2—S1—O1 | 119.60 (18) | C5'—C4'—C3B | 121.5 (4) |
O2—S1—N2 | 105.81 (16) | C5'—C4'—H4' | 119.2 |
O1—S1—N2 | 108.93 (17) | C3B—C4'—H4' | 119.2 |
O2—S1—C11A | 108.81 (18) | C4—C4A—C7A | 119.7 (3) |
O1—S1—C11A | 107.24 (17) | C4—C4A—C3 | 120.9 (3) |
N2—S1—C11A | 105.64 (16) | C7A—C4A—C3 | 119.4 (3) |
C3—N2—S1 | 120.9 (2) | C6'—C5'—C4' | 119.6 (4) |
C3—N2—H2 | 111.8 | C6'—C5'—H5' | 120.2 |
S1—N2—H2 | 112.3 | C4'—C5'—H5' | 120.2 |
C14—N15—C16 | 113.7 (2) | C7'—C6'—C5' | 120.0 (4) |
C14—N15—H15A | 108.8 | C7'—C6'—H6' | 120.0 |
C16—N15—H15A | 108.8 | C5'—C6'—H6' | 120.0 |
C14—N15—H15B | 108.8 | C6'—C7'—C7B | 121.6 (4) |
C16—N15—H15B | 108.8 | C6'—C7'—H7' | 119.2 |
H15A—N15—H15B | 107.7 | C7B—C7'—H7' | 119.2 |
N2—C3—C14 | 109.1 (3) | C4A—C7A—C7 | 118.4 (3) |
N2—C3—C4A | 111.9 (3) | C4A—C7A—C8A | 124.0 (3) |
C14—C3—C4A | 111.5 (3) | C7—C7A—C8A | 117.5 (3) |
N2—C3—H3 | 108.1 | C3B—C7B—C7' | 118.5 (3) |
C14—C3—H3 | 108.1 | C3B—C7B—C8B | 123.2 (3) |
C4A—C3—H3 | 108.1 | C7'—C7B—C8B | 118.1 (3) |
C5—C4—C4A | 120.7 (3) | C9'—C8'—C8B | 120.4 (4) |
C5—C4—H4 | 119.7 | C9'—C8'—H8' | 119.8 |
C4A—C4—H4 | 119.7 | C8B—C8'—H8' | 119.8 |
C6—C5—C4 | 119.6 (3) | C8—C8A—C11A | 116.5 (3) |
C6—C5—H5 | 120.2 | C8—C8A—C7A | 122.1 (3) |
C4—C5—H5 | 120.2 | C11A—C8A—C7A | 121.2 (3) |
C7—C6—C5 | 120.2 (3) | C11B—C8B—C8' | 117.2 (4) |
C7—C6—H6 | 119.9 | C11B—C8B—C7B | 122.7 (3) |
C5—C6—H6 | 119.9 | C8'—C8B—C7B | 119.9 (4) |
C6—C7—C7A | 121.4 (3) | C10'—C9'—C8' | 120.7 (4) |
C6—C7—H7 | 119.3 | C10'—C9'—H9' | 119.7 |
C7A—C7—H7 | 119.3 | C8'—C9'—H9' | 119.7 |
C9—C8—C8A | 121.8 (3) | C9'—C10'—C11' | 119.9 (5) |
C9—C8—H8 | 119.1 | C9'—C10'—H10' | 120.0 |
C8A—C8—H8 | 119.1 | C11'—C10'—H10' | 120.0 |
C10—C9—C8 | 120.4 (4) | C10'—C11'—C11B | 119.1 (5) |
C10—C9—H9 | 119.8 | C10'—C11'—H11' | 120.4 |
C8—C9—H9 | 119.8 | C11B—C11'—H11' | 120.4 |
C9—C10—C11 | 119.8 (4) | C11—C11A—C8A | 122.0 (3) |
C9—C10—H10 | 120.1 | C11—C11A—S1 | 117.9 (3) |
C11—C10—H10 | 120.1 | C8A—C11A—S1 | 120.0 (3) |
C10—C11—C11A | 119.5 (4) | C8B—C11B—C11' | 122.6 (4) |
C10—C11—H11 | 120.2 | C8B—C11B—S1' | 119.6 (3) |
C11A—C11—H11 | 120.2 | C11'—C11B—S1' | 117.7 (3) |
N15—C14—C3 | 113.6 (3) | N15'—C14'—C3' | 113.5 (3) |
N15—C14—H14A | 108.9 | N15'—C14'—H14C | 108.9 |
C3—C14—H14A | 108.9 | C3'—C14'—H14C | 108.9 |
N15—C14—H14B | 108.9 | N15'—C14'—H14D | 108.9 |
C3—C14—H14B | 108.9 | C3'—C14'—H14D | 108.9 |
H14A—C14—H14B | 107.7 | H14C—C14'—H14D | 107.7 |
N15—C16—C18 | 111.8 (3) | C14'—N15'—C16' | 113.0 (3) |
N15—C16—C17 | 108.3 (3) | C14'—N15'—H15C | 109.0 |
C18—C16—C17 | 112.4 (3) | C16'—N15'—H15C | 109.0 |
N15—C16—H16 | 108.1 | C14'—N15'—H15D | 109.0 |
C18—C16—H16 | 108.1 | C16'—N15'—H15D | 109.0 |
C17—C16—H16 | 108.1 | H15C—N15'—H15D | 107.8 |
C16—C17—H17A | 109.5 | N15'—C16'—C18' | 111.5 (3) |
C16—C17—H17B | 109.5 | N15'—C16'—C17' | 108.4 (3) |
H17A—C17—H17B | 109.5 | C18'—C16'—C17' | 112.2 (3) |
C16—C17—H17C | 109.5 | N15'—C16'—H16' | 108.2 |
H17A—C17—H17C | 109.5 | C18'—C16'—H16' | 108.2 |
H17B—C17—H17C | 109.5 | C17'—C16'—H16' | 108.2 |
C19—C18—C25A | 119.7 (3) | C16'—C17'—H17D | 109.5 |
C19—C18—C16 | 121.8 (3) | C16'—C17'—H17E | 109.5 |
C25A—C18—C16 | 118.5 (3) | H17D—C17'—H17E | 109.5 |
C18—C19—C20 | 121.5 (4) | C16'—C17'—H17F | 109.5 |
C18—C19—H19 | 119.2 | H17D—C17'—H17F | 109.5 |
C20—C19—H19 | 119.2 | H17E—C17'—H17F | 109.5 |
C21—C20—C19 | 119.8 (4) | C19'—C18'—C25B | 119.3 (3) |
C21—C20—H20 | 120.1 | C19'—C18'—C16' | 121.1 (3) |
C19—C20—H20 | 120.1 | C25B—C18'—C16' | 119.5 (3) |
C20—C21—C21A | 121.8 (4) | C18'—C19'—C20' | 121.9 (4) |
C20—C21—H21 | 119.1 | C18'—C19'—H19' | 119.1 |
C21A—C21—H21 | 119.1 | C20'—C19'—H19' | 119.1 |
C23—C22—C21A | 120.4 (4) | C21'—C20'—C19' | 120.0 (4) |
C23—C22—H22 | 119.8 | C21'—C20'—H20' | 120.0 |
C21A—C22—H22 | 119.8 | C19'—C20'—H20' | 120.0 |
C22—C23—C24 | 121.3 (4) | C20'—C21'—C21B | 121.5 (4) |
C22—C23—H23 | 119.3 | C20'—C21'—H21' | 119.3 |
C24—C23—H23 | 119.3 | C21B—C21'—H21' | 119.3 |
C25—C24—C23 | 120.1 (4) | C21—C21A—C22 | 122.2 (4) |
C25—C24—H24 | 119.9 | C21—C21A—C25A | 119.1 (3) |
C23—C24—H24 | 119.9 | C22—C21A—C25A | 118.7 (4) |
C24—C25—C25A | 121.4 (4) | C22'—C21B—C21' | 122.4 (4) |
C24—C25—H25 | 119.3 | C22'—C21B—C25B | 119.0 (4) |
C25A—C25—H25 | 119.3 | C21'—C21B—C25B | 118.6 (4) |
O1'—S1'—O2' | 119.8 (2) | C23'—C22'—C21B | 121.1 (5) |
O1'—S1'—N2' | 108.8 (2) | C23'—C22'—H22' | 119.4 |
O2'—S1'—N2' | 105.65 (18) | C21B—C22'—H22' | 119.4 |
O1'—S1'—C11B | 106.76 (19) | C22'—C23'—C24' | 120.0 (4) |
O2'—S1'—C11B | 109.1 (2) | C22'—C23'—H23' | 120.0 |
N2'—S1'—C11B | 105.90 (18) | C24'—C23'—H23' | 120.0 |
N2'—C3'—C3B | 111.9 (3) | C25'—C24'—C23' | 121.1 (5) |
N2'—C3'—C14' | 108.6 (3) | C25'—C24'—H24' | 119.4 |
C3B—C3'—C14' | 110.7 (3) | C23'—C24'—H24' | 119.4 |
N2'—C3'—H3' | 108.5 | C24'—C25'—C25B | 120.7 (4) |
C3B—C3'—H3' | 108.5 | C24'—C25'—H25' | 119.6 |
C14'—C3'—H3' | 108.5 | C25B—C25'—H25' | 119.6 |
C4'—C3B—C7B | 118.7 (3) | C25—C25A—C21A | 118.0 (3) |
C4'—C3B—C3' | 122.0 (3) | C25—C25A—C18 | 124.0 (3) |
C7B—C3B—C3' | 119.4 (3) | C21A—C25A—C18 | 118.0 (3) |
C3'—N2'—S1' | 121.0 (2) | C25'—C25B—C21B | 118.1 (4) |
C3'—N2'—H2' | 119.5 | C25'—C25B—C18' | 123.4 (3) |
S1'—N2'—H2' | 104.4 | C21B—C25B—C18' | 118.5 (4) |
O2—S1—N2—C3 | −157.2 (3) | C8B—C8'—C9'—C10' | 1.1 (6) |
O1—S1—N2—C3 | 73.0 (3) | C8'—C9'—C10'—C11' | 1.9 (7) |
C11A—S1—N2—C3 | −41.9 (3) | C9'—C10'—C11'—C11B | −3.5 (7) |
S1—N2—C3—C14 | −160.9 (2) | C10—C11—C11A—C8A | 1.6 (6) |
S1—N2—C3—C4A | −37.0 (4) | C10—C11—C11A—S1 | −174.9 (3) |
C4A—C4—C5—C6 | −0.2 (6) | C8—C8A—C11A—C11 | 0.9 (5) |
C4—C5—C6—C7 | −0.9 (6) | C7A—C8A—C11A—C11 | −173.2 (3) |
C5—C6—C7—C7A | 0.3 (6) | C8—C8A—C11A—S1 | 177.4 (3) |
C8A—C8—C9—C10 | 1.9 (6) | C7A—C8A—C11A—S1 | 3.2 (4) |
C8—C9—C10—C11 | 0.7 (6) | O2—S1—C11A—C11 | −7.6 (3) |
C9—C10—C11—C11A | −2.5 (6) | O1—S1—C11A—C11 | 123.1 (3) |
C16—N15—C14—C3 | 168.1 (3) | N2—S1—C11A—C11 | −120.8 (3) |
N2—C3—C14—N15 | −78.5 (4) | O2—S1—C11A—C8A | 175.8 (3) |
C4A—C3—C14—N15 | 157.4 (3) | O1—S1—C11A—C8A | −53.5 (3) |
C14—N15—C16—C18 | 55.9 (4) | N2—S1—C11A—C8A | 62.6 (3) |
C14—N15—C16—C17 | −179.8 (3) | C8'—C8B—C11B—C11' | 0.6 (6) |
N15—C16—C18—C19 | 36.1 (4) | C7B—C8B—C11B—C11' | −173.8 (4) |
C17—C16—C18—C19 | −85.9 (4) | C8'—C8B—C11B—S1' | 175.8 (3) |
N15—C16—C18—C25A | −145.7 (3) | C7B—C8B—C11B—S1' | 1.4 (5) |
C17—C16—C18—C25A | 92.2 (4) | C10'—C11'—C11B—C8B | 2.2 (6) |
C25A—C18—C19—C20 | 3.4 (5) | C10'—C11'—C11B—S1' | −173.0 (3) |
C16—C18—C19—C20 | −178.5 (3) | O1'—S1'—C11B—C8B | −52.5 (3) |
C18—C19—C20—C21 | −1.9 (6) | O2'—S1'—C11B—C8B | 176.6 (3) |
C19—C20—C21—C21A | −0.3 (6) | N2'—S1'—C11B—C8B | 63.3 (3) |
C21A—C22—C23—C24 | −1.2 (6) | O1'—S1'—C11B—C11' | 122.9 (3) |
C22—C23—C24—C25 | 0.9 (6) | O2'—S1'—C11B—C11' | −8.0 (4) |
C23—C24—C25—C25A | 0.2 (6) | N2'—S1'—C11B—C11' | −121.3 (3) |
N2'—C3'—C3B—C4' | −105.5 (4) | N2'—C3'—C14'—N15' | −76.7 (4) |
C14'—C3'—C3B—C4' | 15.8 (5) | C3B—C3'—C14'—N15' | 160.1 (3) |
N2'—C3'—C3B—C7B | 75.5 (4) | C3'—C14'—N15'—C16' | 171.8 (3) |
C14'—C3'—C3B—C7B | −163.2 (3) | C14'—N15'—C16'—C18' | 55.2 (4) |
C3B—C3'—N2'—S1' | −39.4 (4) | C14'—N15'—C16'—C17' | 179.2 (3) |
C14'—C3'—N2'—S1' | −161.8 (3) | N15'—C16'—C18'—C19' | 38.7 (4) |
O1'—S1'—N2'—C3' | 74.4 (3) | C17'—C16'—C18'—C19' | −83.2 (4) |
O2'—S1'—N2'—C3' | −155.8 (3) | N15'—C16'—C18'—C25B | −143.2 (3) |
C11B—S1'—N2'—C3' | −40.1 (4) | C17'—C16'—C18'—C25B | 94.9 (4) |
C7B—C3B—C4'—C5' | 2.2 (6) | C25B—C18'—C19'—C20' | 4.1 (6) |
C3'—C3B—C4'—C5' | −176.8 (4) | C16'—C18'—C19'—C20' | −177.8 (3) |
C5—C4—C4A—C7A | 2.0 (6) | C18'—C19'—C20'—C21' | −1.1 (6) |
C5—C4—C4A—C3 | −176.9 (3) | C19'—C20'—C21'—C21B | −2.7 (7) |
N2—C3—C4A—C4 | −105.3 (4) | C20—C21—C21A—C22 | −179.5 (4) |
C14—C3—C4A—C4 | 17.2 (4) | C20—C21—C21A—C25A | 1.1 (6) |
N2—C3—C4A—C7A | 75.9 (4) | C23—C22—C21A—C21 | −179.1 (4) |
C14—C3—C4A—C7A | −161.6 (3) | C23—C22—C21A—C25A | 0.3 (6) |
C3B—C4'—C5'—C6' | −0.8 (7) | C20'—C21'—C21B—C22' | −177.4 (4) |
C4'—C5'—C6'—C7' | −0.5 (7) | C20'—C21'—C21B—C25B | 3.3 (6) |
C5'—C6'—C7'—C7B | 0.3 (7) | C21'—C21B—C22'—C23' | 179.5 (4) |
C4—C4A—C7A—C7 | −2.5 (5) | C25B—C21B—C22'—C23' | −1.2 (6) |
C3—C4A—C7A—C7 | 176.4 (3) | C21B—C22'—C23'—C24' | 1.3 (7) |
C4—C4A—C7A—C8A | 173.1 (3) | C22'—C23'—C24'—C25' | −0.7 (7) |
C3—C4A—C7A—C8A | −8.0 (5) | C23'—C24'—C25'—C25B | 0.0 (6) |
C6—C7—C7A—C4A | 1.4 (5) | C24—C25—C25A—C21A | −0.9 (5) |
C6—C7—C7A—C8A | −174.5 (3) | C24—C25—C25A—C18 | 178.8 (3) |
C4'—C3B—C7B—C7' | −2.3 (5) | C21—C21A—C25A—C25 | −179.8 (3) |
C3'—C3B—C7B—C7' | 176.7 (3) | C22—C21A—C25A—C25 | 0.7 (5) |
C4'—C3B—C7B—C8B | 173.8 (3) | C21—C21A—C25A—C18 | 0.4 (5) |
C3'—C3B—C7B—C8B | −7.2 (5) | C22—C21A—C25A—C18 | −179.1 (3) |
C6'—C7'—C7B—C3B | 1.1 (6) | C19—C18—C25A—C25 | 177.7 (3) |
C6'—C7'—C7B—C8B | −175.2 (4) | C16—C18—C25A—C25 | −0.5 (5) |
C9—C8—C8A—C11A | −2.7 (5) | C19—C18—C25A—C21A | −2.6 (5) |
C9—C8—C8A—C7A | 171.4 (3) | C16—C18—C25A—C21A | 179.2 (3) |
C4A—C7A—C8A—C8 | 137.8 (3) | C24'—C25'—C25B—C21B | 0.1 (5) |
C7—C7A—C8A—C8 | −46.6 (5) | C24'—C25'—C25B—C18' | −179.7 (3) |
C4A—C7A—C8A—C11A | −48.4 (5) | C22'—C21B—C25B—C25' | 0.5 (5) |
C7—C7A—C8A—C11A | 127.2 (3) | C21'—C21B—C25B—C25' | 179.9 (3) |
C9'—C8'—C8B—C11B | −2.3 (5) | C22'—C21B—C25B—C18' | −179.7 (3) |
C9'—C8'—C8B—C7B | 172.3 (3) | C21'—C21B—C25B—C18' | −0.4 (5) |
C3B—C7B—C8B—C11B | −47.6 (5) | C19'—C18'—C25B—C25' | 176.6 (3) |
C7'—C7B—C8B—C11B | 128.4 (4) | C16'—C18'—C25B—C25' | −1.6 (5) |
C3B—C7B—C8B—C8' | 138.1 (4) | C19'—C18'—C25B—C21B | −3.2 (5) |
C7'—C7B—C8B—C8' | −45.8 (5) | C16'—C18'—C25B—C21B | 178.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1i | 0.98 | 2.34 | 3.307 (3) | 167 |
N15—H15B···Cl1 | 0.90 | 2.29 | 3.179 (3) | 168 |
N15—H15A···Cl1i | 0.90 | 2.20 | 3.098 (3) | 174 |
N2′—H2′···Cl1′ | 0.81 | 2.54 | 3.299 (3) | 157 |
N15′—H15C···Cl1′ | 0.90 | 2.18 | 3.072 (3) | 173 |
N15′—H15D···Cl1′ii | 0.90 | 2.31 | 3.185 (3) | 164 |
C7—H7···Cg13 | 0.93 | 2.80 | 3.569 (4) | 140 |
C7′—H7′···Cg4iii | 0.93 | 2.96 | 3.684 (5) | 136 |
C9′—H9′···O1′iii | 0.93 | 2.48 | 3.064 (6) | 121 |
Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x+2, y+1/2, −z+1; (iii) x, y+1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C20H21N2O2S+·Cl− | C26H25N2O2S+·Cl− |
Mr | 388.90 | 464.99 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.230 (2), 10.927 (2), 11.633 (3) | 15.295 (4), 7.764 (3), 20.264 (6) |
α, β, γ (°) | 103.90 (2), 106.62 (3), 96.94 (2) | 90, 100.48 (2), 90 |
V (Å3) | 952.7 (4) | 2366.2 (13) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.28 |
Crystal size (mm) | 0.15 × 0.10 × 0.05 | 0.50 × 0.22 × 0.13 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.88, 0.98 | 0.89, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7330, 5771, 4862 | 14090, 8155, 5732 |
Rint | 0.025 | 0.035 |
(sin θ/λ)max (Å−1) | 0.602 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.095, 1.02 | 0.049, 0.118, 1.01 |
No. of reflections | 5771 | 8155 |
No. of parameters | 472 | 579 |
No. of restraints | 3 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.17 | 0.18, −0.26 |
Absolute structure | Flack (1983), 2356 Friedel pairs | Flack (1983), 3619 Friedel pairs |
Absolute structure parameter | 0.05 (5) | −0.11 (6) |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1 | 0.96 | 2.22 | 3.172 (3) | 173.2 |
N11—H11B···Cl1 | 0.90 | 2.30 | 3.195 (3) | 176.4 |
N11—H11A···Cl1' | 0.90 | 2.22 | 3.049 (2) | 152.5 |
N2'—H2'···Cl1 | 0.95 | 2.39 | 3.154 (3) | 138.1 |
N11'—H11D···Cl1' | 0.90 | 2.20 | 3.067 (3) | 162.6 |
N11'—H11C···Cl1 | 0.90 | 2.34 | 3.229 (3) | 169.9 |
C4—H4···O2'i | 0.98 | 2.36 | 3.114 (4) | 133.4 |
C19—H19···O1ii | 0.93 | 2.60 | 3.465 (7) | 154.7 |
C6'—H6'···O1'iii | 0.93 | 2.47 | 3.234 (5) | 139.4 |
Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1i | 0.98 | 2.34 | 3.307 (3) | 167.1 |
N15—H15B···Cl1 | 0.90 | 2.29 | 3.179 (3) | 167.5 |
N15—H15A···Cl1i | 0.90 | 2.20 | 3.098 (3) | 174.2 |
N2'—H2'···Cl1' | 0.81 | 2.54 | 3.299 (3) | 156.8 |
N15'—H15C···Cl1' | 0.90 | 2.18 | 3.072 (3) | 173.3 |
N15'—H15D···Cl1'ii | 0.90 | 2.31 | 3.185 (3) | 164.3 |
C7—H7···Cg13 | 0.93 | 2.80 | 3.569 (4) | 140.4 |
C7'—H7'···Cg4iii | 0.93 | 2.96 | 3.684 (5) | 135.9 |
C9'—H9'···O1'iii | 0.93 | 2.48 | 3.064 (6) | 120.7 |
Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x+2, y+1/2, −z+1; (iii) x, y+1, z. |
The extracellular calcium sensing receptor (CaSR) (Hofer & Brown, 2003), identified a little over a decade ago (Brown et al., 1993), belongs to family 3 of the G-protein coupled receptors (GPCR). CaSR responds to extracellular calcium levels, thereby maintaining calcium homeostasis in the organism (Brown & MacLeod, 2001). Failure to maintain constant extracellular ionized calcium levels is associated with several disorders, such as hyperparathyroidism and osteoporosis (Brown et al., 1998). Recently, several small synthetic ligands of CaSR have been developed, which act selectively at this receptor as agonists or calcimimetics. These include cinacalcet (Harrington & Fotsch, 2007), presently used clinically, and calindol, developed in our own laboratory (Kessler et al., 2004).
In our continuing search for novel chemical families of CaSR ligands, two cyclic sulfonamide (sultam) compounds, (I) and (II), were recently synthesized using the aziridine-based chemistry developed by our group (Dauban & Dodd, 2000). While the (R)-naphthylethylamine moieties of both these compounds are common to that of calindol and cinacalcet, the sultam rings represent a major structural difference with known CaSR ligands. Compound (I) contains a six-membered sulfonamide ring fused to a benzene ring, and compound (II) contains a seven-membered sulfonamide ring joining the phenyl rings of a biphenyl motif. Furthermore, the attachment of the (R)-naphthylethylamine moiety to the stereogenic benzylic position of the sultam platforms differs in the two compounds by the presence of an additional methylene group in (II).
Compounds (I) and (II) were each obtained as diastereomeric mixtures which could be separated by chromatography. In both cases, only one diastereomer of each compound was observed to be significantly active as a calcimimetic. However, attribution of the absolute configuration at the ring stereogenic center was not possible by the usual NMR techniques. Because suitable crystals of the less active isomers of (I) and (II) could be prepared as hydrochloride salts, X-ray crystallography of these sultams was used to determine their absolute configurations. In both cases, the (R)-naphthylethylamine used for the synthesis of (I) and (II) allowed determination of the absolute configurations assigned here, and which were confirmed by the joint anomalous dispersion effect of the Cl and S atoms present in both crystal structures. Though IUPAC nomenclature conventions attribute (S) and (R) configurations for C4 in (I) and C3 in (II), respectively, both compounds display the same spatial arrangement at the sultam stereogenic centres (Figs. 1 and 2), indicating a strong stereochemical bias by CaSR.
These two compounds crystallized in different Sohncke space groups, viz. P1 for (I) and P21 for (II), in each case having two crystallographically independent molecules, A and B, in the asymmetric unit (Figs. 1 and 2). The two molecules in the asymmetric unit differ primarily in the orientation of the naphthylethylamine fragment with respect to the sulfonamide ring. These differences are more pronounced in (I) than in (II), despite the presence of a linker shorter by one methylene unit. For (I), the overlay of the sulfonamide ring atoms highlights the deviation around the C4—N11 bond, with a change in the C14—C12—N11—C4 torsion angle from -26.9 (4) to 56.3 (4)° (Fig. 3). For (II), the molecules almost superimpose and the N15—C16—C18—C19 torsion angles between the two ring systems are 36.1 (4) and 38.7 (4)° (Fig. 4).
The molecular dimensions in each of the two structures are essentially in agreement with expected values, in particular, those found among the few examples of six-membered and seven-membered sultams [only 32 and six, respectively, reported to date in the Cambridge Structural Database (Version 5.29, January 2008 update; Allen, 2002), despite the widespread biological importance of this family of compounds]. On the basis of the C—N bond distance range of 1.488 (4)–1.551 (4) Å around N11 (N11') for (I) [N15 (N15') for (II)], compounds (I) and (II), characterized as ammonium cations, have their positive charge localized on these N atoms rather than on the sulfonamide atom N2 (N2'). However, each Cl- anion acts as an acceptor for several hydrogen bonds from both types of NH groups, including N2 and N2', and the N···Cl distances are in the expected ranges, 3.064 (6)–3.307 (3) Å (Table 1) (Steiner, 1998).
The asymmetric unit of (I) consists of a µ-chloro-like dimer in which the two chloride ions link the two cations via N—H···Cl hydrogen bonds around a pseudo-inversion centre, forming an R24(8) motif (Bernstein et al., 1995); the amine groups and the two chloride ions form a quasi-square plane lying almost parallel to the naphthalene group, themselves almost parallel to (121), with N11—Cl1(Cl1')—N11' bridging angles equal to 88.5° (94.3°) and Cl1—N11(N11')—Cl1' angles equal to 88.7° (87.8°) [please provide s.u. values]. The anion separation is 4.366 (5) Å.
The cations are composed of two bicyclic units articulated around an ethylamine linker, displaying an overall bent conformation at the amine group. The six-membered sultam unit fused to the benzene ring adopts a half-chair conformation, as assessed by the ring-puckering angles θ and ϕ (Cremer & Pople, 1975), which, for the atom sequence S1/N2/C3/C4/C4A/C5 are 130.5 (4) and 267.1 (5)° for (IA), and 128.3 (4) and 284.3 (5)° for (IB), with atoms N2 and C3 deviating from the S1/C8A/C4A/C4 mean plane by 0.401 (8) and -0.366 (11) Å in (IA), and 0.205 (10) and -0.532 (12) Å in (IB), respectively. The dihedral angles between the mean planes of the two ring systems are equal to 66.3° for (IA) and 60.9° for (IB), implying that the two ring systems are rather maintained orthogonal to each other instead of being oriented face-to-face. Weak intra- and intermolecular edge-to-face interactions and nonconventional C—H···O bonds (only C4—H4···O2'i is reported in Table 1) contribute to stabilize these conformers as head-to-tail dimers, as shown in Fig. 5. The sultam rings lie on top of each other with a centre-to-centre distance above 4 Å along b, and the naphthalene rings are pushed toward the opposite parallel sides. Contiguous dimers then connect into [111] chains by intermolecular offset π–π stacking of their naphthalene ringc sytems. The mean planes of two adjacent naphthalene ring systems are rotated by ~36° relative to each other, barely inclined at 8.38°, and the shortest centroid–centroid distance between two naphthyl moieties is observed to be 3.869 (3) Å. The combination of these different types of interactions generates a sheet lying parallel to (101) (Fig. 5). Single C—H ··· O hydrogen-bonded C(13) and C(7) (Bernstein et al., 1995) chains join, respectively, molecules (IA) and (IB) along the c and a axes (Table 1), thereby generating the three-dimensional framework.
In the crystal structure of (II), the molecules, which comprise a more voluminous sultam moiety linked to the naphthalene ring system via a three-atom arm, exhibit an unfolded conformation. The linker is nearly maximally extended along the a direction of the crystal. The most remote phenyl ring is nearly parallel to the naphthalene group whereas the second one is tilted by ca 51°. The heterocyclic seven-membered ring is in a boat-shaped conformation, with an approximate mirror plane through S1 and the mid-point of the C4A—C7A bond (Fig. 2), with Cremer–Pople puckering angles of θ(2) = 1.103 (3) Å for (IIA) [1.098 (3) Å for (IIB)], θ(3) = 0.179 (3) Å [0.182 (3) Å], ϕ(2) = 352.16 (17) Å [350.52 (19) Å] and ϕ(3) = missing value? [312.3 (11) Å].
Fig. 6 shows the contents of the unit cell, viewed down the b-axis direction. Unlike (I), no intermolecular π–π stacking interactions between rings are present in the crystal structure of (II). However, similarly to (I), the intermolecular organization is dominated by hydrogen-bonding interactions between the Cl- anions and the N atoms (Table 2). The interactions with the amine N15 (N15') N atoms form infinite C22(4) (Bernstein et al., 1995) chains that zigzag around the helicoidal axes in the positions (0, y, 1/2) and (1/2, y, 0), in a trapezoidal fashion parallel to (100). The chloride ions are separated by 4.777 (5) Å and the amine N atoms by 5.082 (5) Å. The N—Cl—N angles range between 79.4 and 108.1°, whereas the Cl—N—Cl angles are between 73.2 and 99.1° [s.u. values?]. The one-dimensional character of the crystal structure is evidenced by the fact that the molecules all lie parallel to (010) and form infinite C(7) (Bernstein et al., 1995) chains via single C—H ···O(sulfonamide) hydrogen bonds extending along [010]. Chains containing the same conformers are related to one another by the 21 screw axes and then held by N—H···Cl interactions. Conformers (IIA) thereby occupy the regions at z ≈ 1/2, 3/2 etc., and conformers (IIB) the regions at z ≈ 0, 1 etc. The resulting columns dovetail with a b/2 spacing being adjacent columns, forming edge-to-face C—H ··· π (arene) contacts directed along a.
In conclusion, the crystal structures of the sultam derivatives (I) and (II) help to shed some light on the possible mode of interaction of these cyclic sulfonamide agonists of the calcium sensing receptor. In particular, these structures must be compared with known arene-type CaSR antagonists (or calcilytics), in which intramolecular π–π stacking has been observed and invoked as an important structural feature for their activity (Gavai et al., 2005; Kessler et al., 2006). In contrast, the crystal structures of both of the CaSR agonists described here revealed a notable absence of this feature between the various aromatic rings. The presence of extended conformations versus horseshoe-like conformations suggests a possible structural parameter that allows differentiation of these two classes of CaSR ligands.