The crystal structures of three solvates of zafirlukast [systematic name: cyclopentyl N-{1-methyl-3-[2-methyl-4-(o-tolylsulfonylaminocarbonyl)benzyl]-1H-indol-5-yl}carbamate], viz. the monohydrate, C31H33N3O6S·H2O, (I), the methanol solvate, C31H33N3O6S·CH3OH, (II), and the ethanol solvate, C31H33N3O6S·C2H5OH, (III), have been determined by single-crystal X-ray diffraction analysis. All three compounds crystallize in the monoclinic crystal system. Zafirlukast adopts a similar Z-shaped conformation in all three solvates. The methanol and ethanol solvates are isostructural. The packing of the zafirlukast molecules in all three crystal structures is similar and is expressed by hydrogen-bonded molecules that are related by translation, along (101) in (I) and along the b axis in (II) and (III). The methanol and ethanol solvent molecules are hydrogen bonded to two molecules of zafirlukast. The water molecule, on the other hand, acts as a connector via hydrogen bonds between three molecules of zafirlukast. The solvent molecules are not released at temperatures below the melting points of the solvates.
Supporting information
CCDC references: 233566; 233567; 233568
All chemicals were of analytical grade and the water used was filtered through a Milli-Q water purification system prior to use. Zafirlukast monohydrate, (I), was recrystallized from a mixture of water and acetone (Ratio?), which are the solvents used in the original patent. Zafirlukast ethanolate, (II), was prepared according to a previously reported procedure. Zafirlukast methanolate, (III), was prepared as follows. Zafirlukast ethanol solvate (2 g, 3.2 mmol) was dissolved in CH2Cl2 150 ml) and the resulting solution was washed with water (3 × 300 ml). The organic layer was separated, dried over anhydrous sodium sulfate and filtered. The filtrate was heated to reflux, methanol (200 ml) was added to the solution, and dichloromethane was distilled off from the stirred mixture until a solid was precipitated. This solid was filtered off, washed on the filter with methanol (2 × 30 ml) and dried under reduced pressure at 333 K. Differential scanning calorimetry (DSC) was employed to characterize the thermal behaviour of the zafirlukast solvates. A Mettler DSC 30 system was used, under a nitrogen atmosphere, at a heating rate of 5 K min−1.
In all three structures, the H atoms were located in difference Fourier maps. The coordinates of the H atoms in the water, methanol and ethanol solvents were freely refined but their bond distances were fixed. The remaining H atoms were constrained riding on their parent atoms, with C—H distances in the range 0.93–0.98 Å and N—H distances of 0.86 Å, and with Uiso(H) = 1.2Ueq(C). Please check added text.
For all compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: Please provide details of software used.
(I) 4-(5-cyclopentyloxycarbonylamino-1-methylindol- 3-ylmethyl)-3-methoxy-
N-(
o-tolylsulfonyl)benzamide monohydrate
top
Crystal data top
C31H33N3O6S·H2O | F(000) = 1256 |
Mr = 593.68 | Dx = 1.320 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2yn | Cell parameters from 16987 reflections |
a = 9.983 (2) Å | θ = 2.2–25.1° |
b = 31.580 (6) Å | µ = 0.16 mm−1 |
c = 10.192 (2) Å | T = 293 K |
β = 111.55 (3)° | Prism, colourless |
V = 2988.6 (12) Å3 | 0.34 × 0.26 × 0.16 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2909 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.080 |
Graphite monochromator | θmax = 25.1°, θmin = 2.2° |
Detector resolution: 95 pixels mm-1 | h = 0→11 |
ϕ scans | k = −37→37 |
16987 measured reflections | l = −12→11 |
5087 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.192 | w = 1/[σ2(Fo2) + (0.1097P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
5087 reflections | Δρmax = 0.42 e Å−3 |
391 parameters | Δρmin = −0.41 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: 0.047 (5) |
Crystal data top
C31H33N3O6S·H2O | V = 2988.6 (12) Å3 |
Mr = 593.68 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.983 (2) Å | µ = 0.16 mm−1 |
b = 31.580 (6) Å | T = 293 K |
c = 10.192 (2) Å | 0.34 × 0.26 × 0.16 mm |
β = 111.55 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2909 reflections with I > 2σ(I) |
16987 measured reflections | Rint = 0.080 |
5087 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.192 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.42 e Å−3 |
5087 reflections | Δρmin = −0.41 e Å−3 |
391 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 1.19327 (8) | 0.07236 (3) | 1.26145 (8) | 0.0690 (4) | |
O1 | −0.1315 (3) | 0.06536 (10) | 0.4198 (3) | 0.1033 (10) | |
O2 | −0.1504 (3) | 0.07721 (9) | 0.6288 (2) | 0.0964 (9) | |
O3 | 0.5368 (2) | 0.12803 (8) | 0.7671 (2) | 0.0746 (7) | |
O4 | 1.0573 (2) | 0.14850 (8) | 1.29929 (19) | 0.0738 (7) | |
O5 | 1.1917 (2) | 0.06807 (9) | 1.3995 (2) | 0.0941 (9) | |
O6 | 1.2097 (2) | 0.03538 (8) | 1.1879 (3) | 0.0866 (7) | |
N1 | −0.0257 (3) | 0.12157 (11) | 0.5397 (2) | 0.0816 (9) | |
H1N1 | −0.0073 | 0.1264 | 0.4650 | 0.098* | |
N2 | 0.2312 (3) | 0.23187 (9) | 0.9791 (2) | 0.0623 (7) | |
N3 | 1.0389 (2) | 0.09303 (9) | 1.1568 (2) | 0.0620 (7) | |
H3N3 | 0.9889 | 0.0800 | 1.0802 | 0.074* | |
C1 | −0.2076 (4) | 0.02298 (14) | 0.4078 (4) | 0.0883 (12) | |
H1C1 | −0.1851 | 0.0086 | 0.4985 | 0.106* | |
C2 | −0.1741 (4) | −0.00318 (14) | 0.3005 (4) | 0.0988 (13) | |
H2A | −0.0749 | 0.0009 | 0.3091 | 0.119* | |
H2B | −0.1896 | −0.0330 | 0.3125 | 0.119* | |
C3 | −0.2745 (6) | 0.01212 (17) | 0.1619 (4) | 0.1202 (16) | |
H3A | −0.2242 | 0.0303 | 0.1185 | 0.144* | |
H3B | −0.3147 | −0.0116 | 0.0994 | 0.144* | |
C4 | −0.3869 (5) | 0.03525 (19) | 0.1859 (5) | 0.139 (2) | |
H4A | −0.4796 | 0.0225 | 0.1333 | 0.167* | |
H4B | −0.3881 | 0.0643 | 0.1547 | 0.167* | |
C5 | −0.3591 (5) | 0.03413 (16) | 0.3400 (5) | 0.1165 (15) | |
H5A | −0.3780 | 0.0616 | 0.3724 | 0.140* | |
H5B | −0.4196 | 0.0131 | 0.3605 | 0.140* | |
C6 | −0.1072 (4) | 0.08735 (14) | 0.5369 (3) | 0.0796 (11) | |
C7 | 0.0323 (3) | 0.15022 (11) | 0.6525 (3) | 0.0640 (9) | |
C8 | 0.1654 (3) | 0.16746 (10) | 0.6755 (3) | 0.0598 (9) | |
H8 | 0.2144 | 0.1606 | 0.6164 | 0.072* | |
C9 | 0.2265 (3) | 0.19527 (10) | 0.7875 (3) | 0.0537 (8) | |
C10 | 0.1480 (3) | 0.20546 (10) | 0.8739 (3) | 0.0544 (8) | |
C11 | 0.0122 (3) | 0.18874 (11) | 0.8482 (3) | 0.0605 (8) | |
H11 | −0.0388 | 0.1960 | 0.9051 | 0.073* | |
C12 | −0.0449 (3) | 0.16150 (11) | 0.7377 (3) | 0.0639 (9) | |
H12 | −0.1362 | 0.1503 | 0.7187 | 0.077* | |
C13 | 0.3618 (3) | 0.21682 (10) | 0.8453 (3) | 0.0569 (8) | |
C14 | 0.3593 (3) | 0.23799 (11) | 0.9608 (3) | 0.0649 (9) | |
H14 | 0.4347 | 0.2545 | 1.0196 | 0.078* | |
C15 | 0.4861 (3) | 0.21420 (11) | 0.7956 (3) | 0.0651 (9) | |
H15A | 0.5162 | 0.2427 | 0.7834 | 0.078* | |
H15B | 0.4540 | 0.2003 | 0.7043 | 0.078* | |
C16 | 0.6136 (3) | 0.19033 (11) | 0.8964 (3) | 0.0556 (8) | |
C17 | 0.6376 (3) | 0.14754 (11) | 0.8793 (3) | 0.0526 (8) | |
C18 | 0.7581 (3) | 0.12678 (11) | 0.9717 (3) | 0.0545 (8) | |
H18 | 0.7754 | 0.0986 | 0.9563 | 0.065* | |
C19 | 0.8524 (3) | 0.14849 (10) | 1.0873 (3) | 0.0508 (8) | |
C20 | 0.8254 (3) | 0.18956 (12) | 1.1102 (3) | 0.0660 (9) | |
H20 | 0.8852 | 0.2035 | 1.1908 | 0.079* | |
C21 | 0.7092 (3) | 0.21062 (11) | 1.0139 (3) | 0.0686 (9) | |
H21 | 0.6950 | 0.2391 | 1.0284 | 0.082* | |
C22 | 0.9886 (3) | 0.13052 (12) | 1.1896 (3) | 0.0585 (9) | |
C23 | 1.3253 (3) | 0.10986 (10) | 1.2668 (3) | 0.0598 (9) | |
C24 | 1.4008 (4) | 0.12775 (13) | 1.3973 (3) | 0.0747 (10) | |
H24 | 1.3751 | 0.1214 | 1.4741 | 0.090* | |
C25 | 1.5127 (4) | 0.15461 (14) | 1.4134 (4) | 0.0947 (13) | |
H25 | 1.5650 | 0.1660 | 1.5016 | 0.114* | |
C26 | 1.5477 (4) | 0.16466 (15) | 1.2998 (5) | 0.0979 (13) | |
H26 | 1.6235 | 0.1831 | 1.3104 | 0.117* | |
C27 | 1.4721 (4) | 0.14776 (13) | 1.1711 (4) | 0.0821 (11) | |
H27 | 1.4975 | 0.1553 | 1.0952 | 0.098* | |
C28 | 1.3577 (3) | 0.11951 (11) | 1.1481 (3) | 0.0600 (8) | |
C29 | 1.2806 (4) | 0.10171 (12) | 1.0041 (3) | 0.0806 (11) | |
H29A | 1.3278 | 0.1108 | 0.9422 | 0.121* | |
H29B | 1.1828 | 0.1115 | 0.9688 | 0.121* | |
H29C | 1.2818 | 0.0713 | 1.0090 | 0.121* | |
C30 | 0.5484 (4) | 0.08360 (14) | 0.7505 (4) | 0.0938 (12) | |
H30A | 0.4603 | 0.0732 | 0.6816 | 0.141* | |
H30B | 0.5659 | 0.0697 | 0.8391 | 0.141* | |
H30C | 0.6267 | 0.0779 | 0.7198 | 0.141* | |
C31 | 0.2005 (4) | 0.24321 (13) | 1.1028 (4) | 0.0861 (12) | |
H31A | 0.2707 | 0.2633 | 1.1582 | 0.129* | |
H31B | 0.2043 | 0.2183 | 1.1581 | 0.129* | |
H31C | 0.1062 | 0.2555 | 1.0741 | 0.129* | |
O7 | 0.9278 (3) | 0.04610 (12) | 0.9032 (3) | 0.0902 (9) | |
H7A | 0.912 (4) | 0.0576 (13) | 0.819 (4) | 0.104 (14)* | |
H7B | 0.891 (6) | 0.0206 (18) | 0.888 (5) | 0.14 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0551 (5) | 0.0823 (8) | 0.0659 (6) | 0.0017 (4) | 0.0178 (4) | 0.0204 (4) |
O1 | 0.110 (2) | 0.135 (3) | 0.0774 (16) | −0.0572 (19) | 0.0499 (14) | −0.0396 (16) |
O2 | 0.123 (2) | 0.105 (2) | 0.0820 (16) | −0.0284 (17) | 0.0619 (16) | −0.0112 (14) |
O3 | 0.0683 (14) | 0.079 (2) | 0.0595 (12) | 0.0019 (12) | 0.0038 (10) | −0.0051 (11) |
O4 | 0.0614 (13) | 0.107 (2) | 0.0514 (12) | −0.0039 (12) | 0.0181 (10) | −0.0177 (12) |
O5 | 0.0776 (16) | 0.135 (2) | 0.0695 (14) | −0.0033 (15) | 0.0268 (11) | 0.0428 (14) |
O6 | 0.0773 (16) | 0.0665 (18) | 0.1091 (18) | 0.0047 (13) | 0.0260 (13) | 0.0002 (14) |
N1 | 0.088 (2) | 0.113 (3) | 0.0527 (15) | −0.0327 (19) | 0.0368 (14) | −0.0153 (15) |
N2 | 0.0582 (16) | 0.070 (2) | 0.0700 (15) | −0.0008 (13) | 0.0363 (12) | −0.0066 (13) |
N3 | 0.0487 (14) | 0.080 (2) | 0.0536 (14) | −0.0005 (14) | 0.0143 (11) | −0.0034 (13) |
C1 | 0.081 (3) | 0.107 (4) | 0.073 (2) | 0.014 (2) | 0.0241 (18) | 0.003 (2) |
C2 | 0.076 (2) | 0.094 (3) | 0.117 (3) | 0.021 (2) | 0.025 (2) | −0.003 (3) |
C3 | 0.137 (4) | 0.132 (5) | 0.081 (3) | 0.021 (3) | 0.028 (3) | −0.018 (3) |
C4 | 0.115 (4) | 0.166 (6) | 0.096 (3) | 0.057 (4) | −0.008 (3) | −0.020 (3) |
C5 | 0.097 (3) | 0.105 (4) | 0.148 (4) | 0.021 (3) | 0.046 (3) | −0.017 (3) |
C6 | 0.077 (2) | 0.111 (3) | 0.057 (2) | −0.014 (2) | 0.0325 (17) | −0.010 (2) |
C7 | 0.066 (2) | 0.083 (3) | 0.0463 (16) | −0.0062 (18) | 0.0247 (14) | 0.0016 (15) |
C8 | 0.0607 (19) | 0.076 (2) | 0.0525 (17) | 0.0013 (17) | 0.0322 (14) | 0.0039 (15) |
C9 | 0.0542 (17) | 0.060 (2) | 0.0540 (16) | 0.0100 (15) | 0.0279 (13) | 0.0103 (14) |
C10 | 0.0513 (17) | 0.061 (2) | 0.0584 (16) | 0.0053 (15) | 0.0286 (13) | 0.0024 (15) |
C11 | 0.0543 (18) | 0.075 (2) | 0.0627 (18) | 0.0044 (17) | 0.0337 (14) | 0.0010 (16) |
C12 | 0.0538 (18) | 0.084 (3) | 0.0594 (17) | −0.0039 (17) | 0.0275 (14) | 0.0013 (17) |
C13 | 0.0501 (17) | 0.061 (2) | 0.0670 (18) | 0.0105 (15) | 0.0301 (14) | 0.0123 (15) |
C14 | 0.0551 (19) | 0.066 (2) | 0.077 (2) | 0.0012 (16) | 0.0289 (15) | −0.0004 (16) |
C15 | 0.0569 (18) | 0.071 (2) | 0.080 (2) | 0.0116 (16) | 0.0399 (15) | 0.0203 (17) |
C16 | 0.0488 (17) | 0.060 (2) | 0.0680 (18) | 0.0057 (16) | 0.0337 (14) | 0.0066 (15) |
C17 | 0.0455 (16) | 0.070 (2) | 0.0443 (15) | −0.0035 (15) | 0.0184 (12) | −0.0005 (14) |
C18 | 0.0505 (17) | 0.065 (2) | 0.0502 (16) | −0.0006 (15) | 0.0214 (13) | −0.0013 (14) |
C19 | 0.0451 (16) | 0.062 (2) | 0.0515 (16) | −0.0050 (15) | 0.0256 (13) | −0.0068 (14) |
C20 | 0.0501 (18) | 0.072 (3) | 0.079 (2) | −0.0117 (17) | 0.0271 (16) | −0.0206 (18) |
C21 | 0.057 (2) | 0.059 (2) | 0.096 (2) | −0.0010 (17) | 0.0355 (18) | −0.0124 (18) |
C22 | 0.0482 (17) | 0.084 (3) | 0.0485 (17) | −0.0073 (17) | 0.0237 (14) | −0.0041 (16) |
C23 | 0.0476 (16) | 0.074 (3) | 0.0587 (18) | 0.0084 (15) | 0.0203 (13) | 0.0085 (15) |
C24 | 0.062 (2) | 0.100 (3) | 0.0610 (19) | −0.003 (2) | 0.0217 (15) | −0.0023 (18) |
C25 | 0.078 (3) | 0.115 (4) | 0.087 (3) | −0.021 (2) | 0.025 (2) | −0.025 (2) |
C26 | 0.081 (3) | 0.098 (4) | 0.120 (3) | −0.024 (2) | 0.043 (3) | −0.019 (3) |
C27 | 0.091 (3) | 0.076 (3) | 0.101 (3) | 0.006 (2) | 0.062 (2) | 0.018 (2) |
C28 | 0.0605 (19) | 0.062 (2) | 0.0626 (18) | 0.0169 (17) | 0.0290 (14) | 0.0128 (15) |
C29 | 0.098 (3) | 0.085 (3) | 0.061 (2) | 0.017 (2) | 0.0317 (18) | 0.0106 (17) |
C30 | 0.096 (3) | 0.084 (3) | 0.077 (2) | −0.017 (2) | 0.0026 (19) | −0.009 (2) |
C31 | 0.085 (2) | 0.101 (3) | 0.088 (2) | −0.007 (2) | 0.0505 (19) | −0.026 (2) |
O7 | 0.113 (2) | 0.086 (2) | 0.0703 (17) | 0.0010 (19) | 0.0312 (14) | −0.0118 (15) |
Geometric parameters (Å, º) top
S1—O5 | 1.419 (2) | C11—H11 | 0.9300 |
S1—O6 | 1.429 (3) | C12—H12 | 0.9300 |
S1—N3 | 1.653 (3) | C13—C14 | 1.362 (4) |
S1—C23 | 1.758 (3) | C13—C15 | 1.505 (4) |
O1—C6 | 1.323 (4) | C14—H14 | 0.9300 |
O1—C1 | 1.521 (5) | C15—C16 | 1.511 (4) |
O2—C6 | 1.210 (4) | C15—H15A | 0.9700 |
O3—C17 | 1.362 (3) | C15—H15B | 0.9700 |
O3—C30 | 1.423 (4) | C16—C21 | 1.384 (4) |
O4—C22 | 1.216 (3) | C16—C17 | 1.394 (4) |
N1—C6 | 1.346 (5) | C17—C18 | 1.389 (4) |
N1—C7 | 1.410 (4) | C18—C19 | 1.390 (4) |
N1—H1N1 | 0.8600 | C18—H18 | 0.9300 |
N2—C10 | 1.371 (4) | C19—C20 | 1.362 (4) |
N2—C14 | 1.373 (4) | C19—C22 | 1.489 (4) |
N2—C31 | 1.447 (4) | C20—C21 | 1.384 (4) |
N3—C22 | 1.374 (4) | C20—H20 | 0.9300 |
N3—H3N3 | 0.8600 | C21—H21 | 0.9300 |
C1—C5 | 1.456 (5) | C23—C24 | 1.386 (4) |
C1—C2 | 1.503 (5) | C23—C28 | 1.396 (4) |
C1—H1C1 | 0.9800 | C24—C25 | 1.364 (5) |
C2—C3 | 1.482 (5) | C24—H24 | 0.9300 |
C2—H2A | 0.9700 | C25—C26 | 1.364 (5) |
C2—H2B | 0.9700 | C25—H25 | 0.9300 |
C3—C4 | 1.433 (6) | C26—C27 | 1.359 (5) |
C3—H3A | 0.9700 | C26—H26 | 0.9300 |
C3—H3B | 0.9700 | C27—C28 | 1.399 (5) |
C4—C5 | 1.492 (6) | C27—H27 | 0.9300 |
C4—H4A | 0.9700 | C28—C29 | 1.494 (4) |
C4—H4B | 0.9700 | C29—H29A | 0.9600 |
C5—H5A | 0.9700 | C29—H29B | 0.9600 |
C5—H5B | 0.9700 | C29—H29C | 0.9600 |
C7—C8 | 1.374 (4) | C30—H30A | 0.9600 |
C7—C12 | 1.403 (4) | C30—H30B | 0.9600 |
C8—C9 | 1.391 (4) | C30—H30C | 0.9600 |
C8—H8 | 0.9300 | C31—H31A | 0.9600 |
C9—C10 | 1.414 (4) | C31—H31B | 0.9600 |
C9—C13 | 1.432 (4) | C31—H31C | 0.9600 |
C10—C11 | 1.387 (4) | O7—H7A | 0.90 (4) |
C11—C12 | 1.364 (4) | O7—H7B | 0.87 (5) |
| | | |
O5—S1—O6 | 119.15 (17) | C14—C13—C15 | 126.7 (3) |
O5—S1—N3 | 109.27 (14) | C9—C13—C15 | 127.2 (3) |
O6—S1—N3 | 104.12 (14) | C13—C14—N2 | 111.2 (3) |
O5—S1—C23 | 108.34 (15) | C13—C14—H14 | 124.4 |
O6—S1—C23 | 109.73 (15) | N2—C14—H14 | 124.4 |
N3—S1—C23 | 105.35 (14) | C13—C15—C16 | 113.0 (2) |
C6—O1—C1 | 117.1 (3) | C13—C15—H15A | 109.0 |
C17—O3—C30 | 118.6 (2) | C16—C15—H15A | 109.0 |
C6—N1—C7 | 126.6 (3) | C13—C15—H15B | 109.0 |
C6—N1—H1N1 | 116.7 | C16—C15—H15B | 109.0 |
C7—N1—H1N1 | 116.7 | H15A—C15—H15B | 107.8 |
C10—N2—C14 | 107.8 (2) | C21—C16—C17 | 117.4 (3) |
C10—N2—C31 | 124.8 (3) | C21—C16—C15 | 119.9 (3) |
C14—N2—C31 | 126.1 (3) | C17—C16—C15 | 122.6 (3) |
C22—N3—S1 | 121.4 (2) | O3—C17—C18 | 123.0 (3) |
C22—N3—H3N3 | 119.3 | O3—C17—C16 | 115.8 (3) |
S1—N3—H3N3 | 119.3 | C18—C17—C16 | 121.2 (3) |
C5—C1—C2 | 105.0 (3) | C19—C18—C17 | 119.4 (3) |
C5—C1—O1 | 103.1 (4) | C19—C18—H18 | 120.3 |
C2—C1—O1 | 107.7 (3) | C17—C18—H18 | 120.3 |
C5—C1—H1C1 | 113.4 | C20—C19—C18 | 120.0 (3) |
C2—C1—H1C1 | 113.4 | C20—C19—C22 | 115.5 (3) |
O1—C1—H1C1 | 113.4 | C18—C19—C22 | 124.5 (3) |
C3—C2—C1 | 105.1 (3) | C19—C20—C21 | 120.2 (3) |
C3—C2—H2A | 110.7 | C19—C20—H20 | 119.9 |
C1—C2—H2A | 110.7 | C21—C20—H20 | 119.9 |
C3—C2—H2B | 110.7 | C20—C21—C16 | 121.5 (3) |
C1—C2—H2B | 110.7 | C20—C21—H21 | 119.2 |
H2A—C2—H2B | 108.8 | C16—C21—H21 | 119.2 |
C4—C3—C2 | 107.5 (3) | O4—C22—N3 | 119.5 (3) |
C4—C3—H3A | 110.2 | O4—C22—C19 | 121.8 (3) |
C2—C3—H3A | 110.2 | N3—C22—C19 | 118.6 (3) |
C4—C3—H3B | 110.2 | C24—C23—C28 | 121.7 (3) |
C2—C3—H3B | 110.2 | C24—C23—S1 | 116.2 (2) |
H3A—C3—H3B | 108.5 | C28—C23—S1 | 122.0 (2) |
C3—C4—C5 | 108.3 (4) | C25—C24—C23 | 120.1 (3) |
C3—C4—H4A | 110.0 | C25—C24—H24 | 119.9 |
C5—C4—H4A | 110.0 | C23—C24—H24 | 119.9 |
C3—C4—H4B | 110.0 | C24—C25—C26 | 119.7 (3) |
C5—C4—H4B | 110.0 | C24—C25—H25 | 120.1 |
H4A—C4—H4B | 108.4 | C26—C25—H25 | 120.1 |
C1—C5—C4 | 105.3 (4) | C27—C26—C25 | 120.2 (4) |
C1—C5—H5A | 110.7 | C27—C26—H26 | 119.9 |
C4—C5—H5A | 110.7 | C25—C26—H26 | 119.9 |
C1—C5—H5B | 110.7 | C26—C27—C28 | 122.8 (3) |
C4—C5—H5B | 110.7 | C26—C27—H27 | 118.6 |
H5A—C5—H5B | 108.8 | C28—C27—H27 | 118.6 |
O2—C6—O1 | 124.0 (4) | C23—C28—C27 | 115.4 (3) |
O2—C6—N1 | 125.5 (3) | C23—C28—C29 | 124.7 (3) |
O1—C6—N1 | 110.5 (3) | C27—C28—C29 | 119.9 (3) |
C8—C7—C12 | 120.7 (3) | C28—C29—H29A | 109.5 |
C8—C7—N1 | 118.4 (3) | C28—C29—H29B | 109.5 |
C12—C7—N1 | 120.9 (3) | H29A—C29—H29B | 109.5 |
C7—C8—C9 | 119.7 (3) | C28—C29—H29C | 109.5 |
C7—C8—H8 | 120.2 | H29A—C29—H29C | 109.5 |
C9—C8—H8 | 120.2 | H29B—C29—H29C | 109.5 |
C8—C9—C10 | 118.6 (3) | O3—C30—H30A | 109.5 |
C8—C9—C13 | 134.5 (2) | O3—C30—H30B | 109.5 |
C10—C9—C13 | 106.9 (3) | H30A—C30—H30B | 109.5 |
N2—C10—C11 | 130.4 (2) | O3—C30—H30C | 109.5 |
N2—C10—C9 | 108.1 (2) | H30A—C30—H30C | 109.5 |
C11—C10—C9 | 121.5 (3) | H30B—C30—H30C | 109.5 |
C12—C11—C10 | 118.6 (3) | N2—C31—H31A | 109.5 |
C12—C11—H11 | 120.7 | N2—C31—H31B | 109.5 |
C10—C11—H11 | 120.7 | H31A—C31—H31B | 109.5 |
C11—C12—C7 | 120.9 (3) | N2—C31—H31C | 109.5 |
C11—C12—H12 | 119.6 | H31A—C31—H31C | 109.5 |
C7—C12—H12 | 119.6 | H31B—C31—H31C | 109.5 |
C14—C13—C9 | 106.0 (2) | H7A—O7—H7B | 107 (4) |
| | | |
O5—S1—N3—C22 | 54.5 (3) | C14—C13—C15—C16 | 66.2 (4) |
O6—S1—N3—C22 | −177.2 (2) | C9—C13—C15—C16 | −108.9 (3) |
C23—S1—N3—C22 | −61.8 (3) | C13—C15—C16—C21 | −81.3 (4) |
C6—O1—C1—C5 | 90.8 (4) | C13—C15—C16—C17 | 96.3 (3) |
C6—O1—C1—C2 | −158.6 (3) | C30—O3—C17—C18 | 5.7 (4) |
C5—C1—C2—C3 | 28.5 (5) | C30—O3—C17—C16 | −174.7 (3) |
O1—C1—C2—C3 | −80.8 (4) | C21—C16—C17—O3 | 176.3 (2) |
C1—C2—C3—C4 | −16.9 (6) | C15—C16—C17—O3 | −1.4 (4) |
C2—C3—C4—C5 | −0.8 (7) | C21—C16—C17—C18 | −4.1 (4) |
C2—C1—C5—C4 | −28.9 (5) | C15—C16—C17—C18 | 178.2 (2) |
O1—C1—C5—C4 | 83.8 (4) | O3—C17—C18—C19 | −177.1 (2) |
C3—C4—C5—C1 | 18.9 (6) | C16—C17—C18—C19 | 3.3 (4) |
C1—O1—C6—O2 | −5.4 (6) | C17—C18—C19—C20 | 0.8 (4) |
C1—O1—C6—N1 | 173.2 (3) | C17—C18—C19—C22 | −176.8 (2) |
C7—N1—C6—O2 | 4.6 (7) | C18—C19—C20—C21 | −4.1 (4) |
C7—N1—C6—O1 | −174.0 (3) | C22—C19—C20—C21 | 173.7 (3) |
C6—N1—C7—C8 | 144.7 (4) | C19—C20—C21—C16 | 3.3 (5) |
C6—N1—C7—C12 | −36.4 (5) | C17—C16—C21—C20 | 0.8 (4) |
C12—C7—C8—C9 | 2.2 (5) | C15—C16—C21—C20 | 178.5 (3) |
N1—C7—C8—C9 | −178.9 (3) | S1—N3—C22—O4 | −1.7 (4) |
C7—C8—C9—C10 | −0.8 (4) | S1—N3—C22—C19 | 176.99 (19) |
C7—C8—C9—C13 | 176.3 (3) | C20—C19—C22—O4 | 12.6 (4) |
C14—N2—C10—C11 | 177.9 (3) | C18—C19—C22—O4 | −169.7 (3) |
C31—N2—C10—C11 | 10.1 (5) | C20—C19—C22—N3 | −166.0 (3) |
C14—N2—C10—C9 | −0.5 (3) | C18—C19—C22—N3 | 11.7 (4) |
C31—N2—C10—C9 | −168.3 (3) | O5—S1—C23—C24 | 0.0 (3) |
C8—C9—C10—N2 | 177.8 (3) | O6—S1—C23—C24 | −131.6 (3) |
C13—C9—C10—N2 | 0.0 (3) | N3—S1—C23—C24 | 116.9 (3) |
C8—C9—C10—C11 | −0.7 (4) | O5—S1—C23—C28 | 176.8 (3) |
C13—C9—C10—C11 | −178.5 (3) | O6—S1—C23—C28 | 45.2 (3) |
N2—C10—C11—C12 | −177.4 (3) | N3—S1—C23—C28 | −66.4 (3) |
C9—C10—C11—C12 | 0.8 (4) | C28—C23—C24—C25 | −1.9 (5) |
C10—C11—C12—C7 | 0.6 (5) | S1—C23—C24—C25 | 174.8 (3) |
C8—C7—C12—C11 | −2.2 (5) | C23—C24—C25—C26 | 1.7 (6) |
N1—C7—C12—C11 | 179.0 (3) | C24—C25—C26—C27 | −0.5 (7) |
C8—C9—C13—C14 | −176.8 (3) | C25—C26—C27—C28 | −0.5 (7) |
C10—C9—C13—C14 | 0.5 (3) | C24—C23—C28—C27 | 0.9 (5) |
C8—C9—C13—C15 | −0.9 (5) | S1—C23—C28—C27 | −175.7 (3) |
C10—C9—C13—C15 | 176.5 (3) | C24—C23—C28—C29 | −179.6 (3) |
C9—C13—C14—N2 | −0.8 (4) | S1—C23—C28—C29 | 3.8 (4) |
C15—C13—C14—N2 | −176.8 (3) | C26—C27—C28—C23 | 0.3 (5) |
C10—N2—C14—C13 | 0.9 (4) | C26—C27—C28—C29 | −179.2 (4) |
C31—N2—C14—C13 | 168.4 (3) | | |
(II) 4-(5-cyclopentyloxycarbonylamino-1-methylindol- 3-ylmethyl)-3-methoxy-
N-(
o-tolylsulfonyl)benzamide methanol solvate
top
Crystal data top
C31H33N3O6S·CH4O | F(000) = 1288 |
Mr = 607.71 | Dx = 1.297 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: C -2yc | Cell parameters from 13868 reflections |
a = 17.002 (3) Å | θ = 2.2–17.1° |
b = 11.111 (2) Å | µ = 0.16 mm−1 |
c = 17.129 (3) Å | T = 293 K |
β = 105.94 (2)° | Plate, colourless |
V = 3111.4 (10) Å3 | 0.39 × 0.33 × 0.03 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1811 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.4°, θmin = 2.2° |
Detector resolution: 95 pixels mm-1 | h = 0→20 |
ϕ scans | k = 0→13 |
2839 measured reflections | l = −20→19 |
2839 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0792P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2839 reflections | Δρmax = 0.29 e Å−3 |
396 parameters | Δρmin = −0.17 e Å−3 |
2 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: 0.0052 (10) |
Crystal data top
C31H33N3O6S·CH4O | V = 3111.4 (10) Å3 |
Mr = 607.71 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 17.002 (3) Å | µ = 0.16 mm−1 |
b = 11.111 (2) Å | T = 293 K |
c = 17.129 (3) Å | 0.39 × 0.33 × 0.03 mm |
β = 105.94 (2)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1811 reflections with I > 2σ(I) |
2839 measured reflections | Rint = 0.000 |
2839 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 2 restraints |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.29 e Å−3 |
2839 reflections | Δρmin = −0.17 e Å−3 |
396 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.31400 (10) | −0.11710 (12) | 0.30000 (9) | 0.0760 (5) | |
O1 | 0.0645 (3) | 1.0019 (5) | 0.3078 (4) | 0.122 (2) | |
O2 | −0.0420 (4) | 0.8869 (6) | 0.3148 (4) | 0.131 (2) | |
O3 | 0.2510 (3) | 0.4618 (3) | 0.4068 (2) | 0.0755 (11) | |
O4 | 0.2650 (2) | −0.0764 (3) | 0.4480 (3) | 0.0792 (11) | |
O5 | 0.3382 (3) | −0.0810 (4) | 0.2295 (2) | 0.0932 (14) | |
O6 | 0.2433 (3) | −0.1897 (4) | 0.2894 (3) | 0.1020 (15) | |
N1 | 0.0858 (3) | 0.8623 (5) | 0.4007 (4) | 0.099 (2) | |
H41 | 0.1347 | 0.8908 | 0.4114 | 0.119* | |
N2 | 0.0584 (3) | 0.4882 (5) | 0.6010 (3) | 0.0820 (14) | |
N3 | 0.3011 (3) | 0.0113 (4) | 0.3434 (3) | 0.0647 (12) | |
H42 | 0.3093 | 0.0775 | 0.3209 | 0.078* | |
C1 | 0.0096 (6) | 1.0737 (10) | 0.2383 (6) | 0.127 (3) | |
H1 | −0.0459 | 1.0852 | 0.2436 | 0.152* | |
C2 | 0.0119 (7) | 1.0049 (11) | 0.1715 (8) | 0.149 (4) | |
H2A | −0.0366 | 1.0193 | 0.1271 | 0.179* | |
H2B | 0.0141 | 0.9200 | 0.1851 | 0.179* | |
C3 | 0.0883 (6) | 1.0414 (7) | 0.1470 (5) | 0.110 (3) | |
H3A | 0.1304 | 0.9802 | 0.1631 | 0.131* | |
H3B | 0.0757 | 1.0529 | 0.0887 | 0.131* | |
C4 | 0.1158 (5) | 1.1561 (7) | 0.1905 (5) | 0.099 (2) | |
H4A | 0.1682 | 1.1451 | 0.2304 | 0.119* | |
H4B | 0.1216 | 1.2179 | 0.1525 | 0.119* | |
C5 | 0.0531 (6) | 1.1914 (7) | 0.2309 (5) | 0.113 (3) | |
H5A | 0.0153 | 1.2495 | 0.1984 | 0.136* | |
H5B | 0.0780 | 1.2259 | 0.2840 | 0.136* | |
C6 | 0.0298 (5) | 0.9130 (7) | 0.3394 (5) | 0.102 (2) | |
C7 | 0.0728 (4) | 0.7668 (6) | 0.4495 (4) | 0.0776 (17) | |
C8 | 0.1376 (3) | 0.6905 (5) | 0.4823 (4) | 0.0693 (15) | |
H8 | 0.1872 | 0.7017 | 0.4702 | 0.083* | |
C9 | 0.1291 (3) | 0.5977 (5) | 0.5329 (3) | 0.0639 (14) | |
C10 | 0.0525 (4) | 0.5846 (5) | 0.5498 (4) | 0.0700 (16) | |
C11 | −0.0124 (4) | 0.6630 (7) | 0.5181 (4) | 0.0840 (19) | |
H11 | −0.0620 | 0.6539 | 0.5305 | 0.101* | |
C12 | −0.0011 (4) | 0.7532 (6) | 0.4687 (4) | 0.0845 (19) | |
H12 | −0.0436 | 0.8068 | 0.4472 | 0.101* | |
C13 | 0.1805 (4) | 0.5032 (5) | 0.5757 (3) | 0.0657 (14) | |
C14 | 0.1350 (4) | 0.4380 (6) | 0.6152 (3) | 0.0748 (16) | |
H14 | 0.1530 | 0.3702 | 0.6468 | 0.090* | |
C15 | 0.2664 (4) | 0.4737 (5) | 0.5731 (3) | 0.0697 (15) | |
H15A | 0.2870 | 0.5387 | 0.5464 | 0.084* | |
H15B | 0.3015 | 0.4675 | 0.6282 | 0.084* | |
C16 | 0.2702 (3) | 0.3588 (5) | 0.5293 (3) | 0.0604 (14) | |
C17 | 0.2617 (3) | 0.3526 (4) | 0.4458 (3) | 0.0564 (13) | |
C18 | 0.2654 (3) | 0.2446 (4) | 0.4073 (3) | 0.0595 (13) | |
H18 | 0.2632 | 0.2434 | 0.3525 | 0.071* | |
C19 | 0.2724 (3) | 0.1365 (4) | 0.4511 (3) | 0.0583 (13) | |
C20 | 0.2775 (3) | 0.1410 (5) | 0.5328 (3) | 0.0684 (15) | |
H20 | 0.2808 | 0.0698 | 0.5621 | 0.082* | |
C21 | 0.2779 (4) | 0.2508 (5) | 0.5718 (3) | 0.0707 (15) | |
H21 | 0.2833 | 0.2520 | 0.6273 | 0.085* | |
C22 | 0.2774 (3) | 0.0170 (5) | 0.4152 (4) | 0.0635 (15) | |
C23 | 0.3951 (3) | −0.1892 (4) | 0.3693 (3) | 0.0615 (14) | |
C24 | 0.3783 (4) | −0.2927 (5) | 0.4058 (4) | 0.0787 (18) | |
H24 | 0.3245 | −0.3190 | 0.3958 | 0.094* | |
C25 | 0.4400 (5) | −0.3574 (7) | 0.4569 (5) | 0.097 (2) | |
H25 | 0.4280 | −0.4277 | 0.4808 | 0.116* | |
C26 | 0.5182 (6) | −0.3193 (7) | 0.4727 (5) | 0.100 (2) | |
H26 | 0.5598 | −0.3638 | 0.5073 | 0.120* | |
C27 | 0.5370 (4) | −0.2154 (7) | 0.4380 (4) | 0.087 (2) | |
H27 | 0.5911 | −0.1899 | 0.4503 | 0.105* | |
C28 | 0.4761 (4) | −0.1471 (5) | 0.3844 (3) | 0.0684 (15) | |
C29 | 0.5006 (4) | −0.0346 (6) | 0.3469 (4) | 0.090 (2) | |
H29A | 0.5590 | −0.0265 | 0.3635 | 0.135* | |
H29B | 0.4761 | 0.0344 | 0.3645 | 0.135* | |
H29C | 0.4820 | −0.0405 | 0.2888 | 0.135* | |
C30 | 0.2386 (5) | 0.4621 (5) | 0.3207 (4) | 0.089 (2) | |
H30A | 0.2253 | 0.5421 | 0.3001 | 0.134* | |
H30B | 0.1944 | 0.4087 | 0.2958 | 0.134* | |
H30C | 0.2876 | 0.4356 | 0.3084 | 0.134* | |
C31 | −0.0107 (6) | 0.4319 (8) | 0.6251 (5) | 0.110 (3) | |
H31A | 0.0103 | 0.3749 | 0.6679 | 0.165* | |
H31B | −0.0460 | 0.3914 | 0.5792 | 0.165* | |
H31C | −0.0411 | 0.4931 | 0.6438 | 0.165* | |
O7 | 0.3505 (4) | 0.2032 (4) | 0.2591 (3) | 0.0983 (16) | |
H43 | 0.377 (5) | 0.262 (8) | 0.277 (5) | 0.118* | |
C32 | 0.3232 (5) | 0.2186 (7) | 0.1761 (5) | 0.102 (2) | |
H32A | 0.3689 | 0.2347 | 0.1550 | 0.154* | |
H32B | 0.2857 | 0.2850 | 0.1639 | 0.154* | |
H32C | 0.2960 | 0.1467 | 0.1515 | 0.154* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0848 (10) | 0.0572 (8) | 0.0725 (10) | −0.0011 (8) | −0.0014 (8) | −0.0113 (7) |
O1 | 0.091 (3) | 0.124 (4) | 0.127 (4) | −0.024 (3) | −0.007 (3) | 0.053 (4) |
O2 | 0.081 (3) | 0.135 (4) | 0.152 (5) | −0.027 (3) | −0.009 (3) | 0.027 (4) |
O3 | 0.104 (3) | 0.051 (2) | 0.067 (2) | 0.0017 (19) | 0.017 (2) | 0.0051 (18) |
O4 | 0.081 (3) | 0.057 (2) | 0.103 (3) | −0.0023 (19) | 0.031 (2) | 0.008 (2) |
O5 | 0.142 (4) | 0.083 (3) | 0.047 (2) | 0.010 (3) | 0.013 (2) | −0.004 (2) |
O6 | 0.083 (3) | 0.073 (3) | 0.127 (4) | −0.016 (2) | −0.011 (3) | −0.014 (3) |
N1 | 0.061 (3) | 0.084 (4) | 0.138 (5) | −0.010 (3) | 0.004 (3) | 0.033 (4) |
N2 | 0.079 (4) | 0.097 (4) | 0.079 (3) | −0.014 (3) | 0.038 (3) | −0.014 (3) |
N3 | 0.078 (3) | 0.048 (2) | 0.066 (3) | −0.001 (2) | 0.016 (2) | −0.003 (2) |
C1 | 0.112 (7) | 0.163 (8) | 0.112 (7) | −0.025 (6) | 0.040 (5) | −0.014 (7) |
C2 | 0.164 (11) | 0.137 (8) | 0.144 (9) | −0.048 (7) | 0.039 (8) | −0.010 (7) |
C3 | 0.128 (7) | 0.104 (6) | 0.093 (5) | 0.013 (5) | 0.024 (5) | −0.003 (4) |
C4 | 0.095 (5) | 0.107 (5) | 0.086 (5) | −0.002 (4) | 0.009 (4) | 0.012 (4) |
C5 | 0.152 (8) | 0.085 (5) | 0.095 (5) | 0.010 (5) | 0.022 (5) | 0.007 (4) |
C6 | 0.075 (5) | 0.097 (5) | 0.125 (6) | −0.021 (4) | 0.012 (4) | 0.013 (5) |
C7 | 0.063 (4) | 0.074 (4) | 0.093 (4) | −0.006 (3) | 0.015 (3) | −0.003 (3) |
C8 | 0.058 (3) | 0.072 (4) | 0.079 (4) | −0.017 (3) | 0.020 (3) | 0.002 (3) |
C9 | 0.060 (3) | 0.068 (3) | 0.065 (3) | −0.010 (3) | 0.018 (3) | −0.011 (3) |
C10 | 0.084 (4) | 0.064 (3) | 0.068 (4) | −0.017 (3) | 0.031 (3) | −0.011 (3) |
C11 | 0.058 (4) | 0.089 (4) | 0.108 (5) | −0.004 (3) | 0.026 (3) | −0.020 (4) |
C12 | 0.059 (4) | 0.086 (4) | 0.109 (5) | −0.006 (3) | 0.023 (3) | −0.009 (4) |
C13 | 0.065 (3) | 0.072 (3) | 0.061 (3) | −0.006 (3) | 0.020 (3) | −0.014 (3) |
C14 | 0.094 (5) | 0.072 (4) | 0.063 (4) | −0.013 (4) | 0.028 (3) | −0.008 (3) |
C15 | 0.074 (4) | 0.075 (3) | 0.056 (3) | 0.005 (3) | 0.012 (3) | −0.010 (3) |
C16 | 0.056 (3) | 0.061 (3) | 0.062 (3) | 0.005 (2) | 0.014 (2) | 0.003 (2) |
C17 | 0.048 (3) | 0.055 (3) | 0.062 (3) | −0.001 (2) | 0.008 (2) | 0.005 (2) |
C18 | 0.054 (3) | 0.060 (3) | 0.060 (3) | −0.002 (2) | 0.007 (2) | 0.009 (3) |
C19 | 0.054 (3) | 0.055 (3) | 0.063 (3) | 0.000 (2) | 0.010 (2) | 0.006 (2) |
C20 | 0.068 (4) | 0.072 (4) | 0.067 (4) | 0.011 (3) | 0.023 (3) | 0.021 (3) |
C21 | 0.089 (4) | 0.074 (4) | 0.053 (3) | 0.021 (3) | 0.025 (3) | 0.010 (3) |
C22 | 0.051 (3) | 0.057 (3) | 0.077 (4) | −0.005 (2) | 0.008 (3) | 0.005 (3) |
C23 | 0.067 (4) | 0.047 (3) | 0.068 (3) | 0.000 (2) | 0.016 (3) | −0.010 (2) |
C24 | 0.087 (4) | 0.057 (3) | 0.088 (4) | −0.001 (3) | 0.017 (4) | 0.003 (3) |
C25 | 0.095 (6) | 0.083 (4) | 0.111 (6) | 0.006 (4) | 0.027 (4) | 0.021 (4) |
C26 | 0.119 (7) | 0.096 (5) | 0.083 (5) | 0.032 (5) | 0.024 (4) | 0.028 (4) |
C27 | 0.064 (4) | 0.117 (6) | 0.077 (4) | 0.013 (4) | 0.013 (3) | −0.007 (4) |
C28 | 0.088 (4) | 0.072 (3) | 0.050 (3) | −0.006 (3) | 0.026 (3) | −0.009 (3) |
C29 | 0.095 (5) | 0.087 (4) | 0.089 (5) | −0.021 (3) | 0.027 (4) | −0.009 (4) |
C30 | 0.134 (6) | 0.064 (4) | 0.062 (4) | −0.003 (4) | 0.014 (4) | 0.015 (3) |
C31 | 0.129 (7) | 0.117 (6) | 0.102 (5) | −0.039 (5) | 0.064 (5) | −0.021 (5) |
O7 | 0.134 (4) | 0.083 (3) | 0.083 (3) | −0.024 (3) | 0.038 (3) | 0.012 (2) |
C32 | 0.103 (5) | 0.113 (6) | 0.097 (6) | 0.022 (4) | 0.038 (4) | 0.022 (4) |
Geometric parameters (Å, º) top
S1—O6 | 1.417 (5) | C13—C14 | 1.367 (8) |
S1—O5 | 1.437 (5) | C13—C15 | 1.509 (8) |
S1—N3 | 1.651 (5) | C14—H14 | 0.9300 |
S1—C23 | 1.748 (5) | C15—C16 | 1.491 (8) |
O1—C6 | 1.338 (9) | C15—H15A | 0.9700 |
O1—C1 | 1.521 (11) | C15—H15B | 0.9700 |
O2—C6 | 1.212 (9) | C16—C21 | 1.392 (7) |
O3—C17 | 1.372 (6) | C16—C17 | 1.400 (7) |
O3—C30 | 1.432 (7) | C17—C18 | 1.378 (7) |
O4—C22 | 1.225 (6) | C18—C19 | 1.404 (7) |
N1—C6 | 1.333 (9) | C18—H18 | 0.9300 |
N1—C7 | 1.405 (8) | C19—C20 | 1.379 (8) |
N1—H41 | 0.8600 | C19—C22 | 1.475 (8) |
N2—C10 | 1.371 (8) | C20—C21 | 1.390 (8) |
N2—C14 | 1.376 (8) | C20—H20 | 0.9300 |
N2—C31 | 1.486 (9) | C21—H21 | 0.9300 |
N3—C22 | 1.396 (7) | C23—C24 | 1.376 (8) |
N3—H42 | 0.8600 | C23—C28 | 1.410 (8) |
C1—C2 | 1.385 (13) | C24—C25 | 1.371 (9) |
C1—C5 | 1.525 (12) | C24—H24 | 0.9300 |
C1—H1 | 0.9800 | C25—C26 | 1.350 (11) |
C2—C3 | 1.526 (12) | C25—H25 | 0.9300 |
C2—H2A | 0.9700 | C26—C27 | 1.376 (10) |
C2—H2B | 0.9700 | C26—H26 | 0.9300 |
C3—C4 | 1.486 (11) | C27—C28 | 1.402 (8) |
C3—H3A | 0.9700 | C27—H27 | 0.9300 |
C3—H3B | 0.9700 | C28—C29 | 1.515 (9) |
C4—C5 | 1.475 (12) | C29—H29A | 0.9600 |
C4—H4A | 0.9700 | C29—H29B | 0.9600 |
C4—H4B | 0.9700 | C29—H29C | 0.9600 |
C5—H5A | 0.9700 | C30—H30A | 0.9600 |
C5—H5B | 0.9700 | C30—H30B | 0.9600 |
C7—C8 | 1.382 (8) | C30—H30C | 0.9600 |
C7—C12 | 1.392 (9) | C31—H31A | 0.9600 |
C8—C9 | 1.379 (8) | C31—H31B | 0.9600 |
C8—H8 | 0.9300 | C31—H31C | 0.9600 |
C9—C10 | 1.417 (8) | O7—C32 | 1.381 (9) |
C9—C13 | 1.432 (8) | O7—H43 | 0.81 (9) |
C10—C11 | 1.394 (9) | C32—H32A | 0.9600 |
C11—C12 | 1.360 (10) | C32—H32B | 0.9600 |
C11—H11 | 0.9300 | C32—H32C | 0.9600 |
C12—H12 | 0.9300 | | |
| | | |
O6—S1—O5 | 118.7 (3) | C13—C14—H14 | 125.2 |
O6—S1—N3 | 109.7 (3) | N2—C14—H14 | 125.2 |
O5—S1—N3 | 104.0 (3) | C16—C15—C13 | 112.1 (5) |
O6—S1—C23 | 108.0 (3) | C16—C15—H15A | 109.2 |
O5—S1—C23 | 110.1 (3) | C13—C15—H15A | 109.2 |
N3—S1—C23 | 105.6 (2) | C16—C15—H15B | 109.2 |
C6—O1—C1 | 117.4 (6) | C13—C15—H15B | 109.2 |
C17—O3—C30 | 117.7 (4) | H15A—C15—H15B | 107.9 |
C6—N1—C7 | 126.3 (6) | C21—C16—C17 | 117.4 (5) |
C6—N1—H41 | 116.8 | C21—C16—C15 | 119.1 (5) |
C7—N1—H41 | 116.8 | C17—C16—C15 | 123.4 (5) |
C10—N2—C14 | 109.1 (5) | O3—C17—C18 | 123.7 (5) |
C10—N2—C31 | 125.7 (6) | O3—C17—C16 | 114.5 (4) |
C14—N2—C31 | 124.3 (6) | C18—C17—C16 | 121.8 (5) |
C22—N3—S1 | 122.9 (4) | C17—C18—C19 | 119.9 (5) |
C22—N3—H42 | 118.6 | C17—C18—H18 | 120.1 |
S1—N3—H42 | 118.6 | C19—C18—H18 | 120.1 |
C2—C1—O1 | 101.9 (10) | C20—C19—C18 | 118.9 (5) |
C2—C1—C5 | 106.3 (8) | C20—C19—C22 | 117.4 (5) |
O1—C1—C5 | 107.9 (7) | C18—C19—C22 | 123.6 (5) |
C2—C1—H1 | 113.3 | C19—C20—C21 | 120.7 (5) |
O1—C1—H1 | 113.3 | C19—C20—H20 | 119.7 |
C5—C1—H1 | 113.3 | C21—C20—H20 | 119.7 |
C1—C2—C3 | 107.5 (8) | C20—C21—C16 | 121.2 (5) |
C1—C2—H2A | 110.2 | C20—C21—H21 | 119.4 |
C3—C2—H2A | 110.2 | C16—C21—H21 | 119.4 |
C1—C2—H2B | 110.2 | O4—C22—N3 | 119.5 (5) |
C3—C2—H2B | 110.2 | O4—C22—C19 | 122.3 (6) |
H2A—C2—H2B | 108.5 | N3—C22—C19 | 118.1 (5) |
C4—C3—C2 | 105.3 (8) | C24—C23—C28 | 120.6 (5) |
C4—C3—H3A | 110.7 | C24—C23—S1 | 117.9 (4) |
C2—C3—H3A | 110.7 | C28—C23—S1 | 121.5 (4) |
C4—C3—H3B | 110.7 | C25—C24—C23 | 120.7 (6) |
C2—C3—H3B | 110.7 | C25—C24—H24 | 119.7 |
H3A—C3—H3B | 108.8 | C23—C24—H24 | 119.7 |
C5—C4—C3 | 107.2 (7) | C26—C25—C24 | 120.2 (7) |
C5—C4—H4A | 110.3 | C26—C25—H25 | 119.9 |
C3—C4—H4A | 110.3 | C24—C25—H25 | 119.9 |
C5—C4—H4B | 110.3 | C25—C26—C27 | 120.6 (7) |
C3—C4—H4B | 110.3 | C25—C26—H26 | 119.7 |
H4A—C4—H4B | 108.5 | C27—C26—H26 | 119.7 |
C4—C5—C1 | 103.9 (7) | C26—C27—C28 | 121.3 (6) |
C4—C5—H5A | 111.0 | C26—C27—H27 | 119.3 |
C1—C5—H5A | 111.0 | C28—C27—H27 | 119.3 |
C4—C5—H5B | 111.0 | C27—C28—C23 | 116.7 (6) |
C1—C5—H5B | 111.0 | C27—C28—C29 | 119.0 (6) |
H5A—C5—H5B | 109.0 | C23—C28—C29 | 124.3 (5) |
O2—C6—N1 | 127.3 (8) | C28—C29—H29A | 109.5 |
O2—C6—O1 | 123.3 (7) | C28—C29—H29B | 109.5 |
N1—C6—O1 | 109.3 (6) | H29A—C29—H29B | 109.5 |
C8—C7—C12 | 120.6 (6) | C28—C29—H29C | 109.5 |
C8—C7—N1 | 117.8 (6) | H29A—C29—H29C | 109.5 |
C12—C7—N1 | 121.5 (6) | H29B—C29—H29C | 109.5 |
C9—C8—C7 | 120.3 (6) | O3—C30—H30A | 109.5 |
C9—C8—H8 | 119.9 | O3—C30—H30B | 109.5 |
C7—C8—H8 | 119.9 | H30A—C30—H30B | 109.5 |
C8—C9—C10 | 117.8 (5) | O3—C30—H30C | 109.5 |
C8—C9—C13 | 135.6 (6) | H30A—C30—H30C | 109.5 |
C10—C9—C13 | 106.6 (5) | H30B—C30—H30C | 109.5 |
N2—C10—C11 | 130.4 (6) | N2—C31—H31A | 109.5 |
N2—C10—C9 | 107.6 (5) | N2—C31—H31B | 109.5 |
C11—C10—C9 | 122.0 (6) | H31A—C31—H31B | 109.5 |
C12—C11—C10 | 118.1 (6) | N2—C31—H31C | 109.5 |
C12—C11—H11 | 120.9 | H31A—C31—H31C | 109.5 |
C10—C11—H11 | 120.9 | H31B—C31—H31C | 109.5 |
C11—C12—C7 | 121.2 (6) | C32—O7—H43 | 106 (6) |
C11—C12—H12 | 119.4 | O7—C32—H32A | 109.5 |
C7—C12—H12 | 119.4 | O7—C32—H32B | 109.5 |
C14—C13—C9 | 107.0 (5) | H32A—C32—H32B | 109.5 |
C14—C13—C15 | 125.7 (6) | O7—C32—H32C | 109.5 |
C9—C13—C15 | 127.1 (6) | H32A—C32—H32C | 109.5 |
C13—C14—N2 | 109.6 (6) | H32B—C32—H32C | 109.5 |
| | | |
O6—S1—N3—C22 | 52.4 (4) | C14—C13—C15—C16 | 65.3 (7) |
O5—S1—N3—C22 | −179.7 (4) | C9—C13—C15—C16 | −109.5 (6) |
C23—S1—N3—C22 | −63.7 (4) | C13—C15—C16—C21 | −85.9 (6) |
C6—O1—C1—C2 | −86.5 (9) | C13—C15—C16—C17 | 90.3 (7) |
C6—O1—C1—C5 | 161.8 (8) | C30—O3—C17—C18 | 3.5 (8) |
O1—C1—C2—C3 | −84.3 (10) | C30—O3—C17—C16 | −177.5 (5) |
C5—C1—C2—C3 | 28.6 (12) | C21—C16—C17—O3 | 177.4 (5) |
C1—C2—C3—C4 | −14.6 (11) | C15—C16—C17—O3 | 1.2 (7) |
C2—C3—C4—C5 | −6.0 (9) | C21—C16—C17—C18 | −3.6 (7) |
C3—C4—C5—C1 | 22.3 (8) | C15—C16—C17—C18 | −179.8 (5) |
C2—C1—C5—C4 | −32.1 (10) | O3—C17—C18—C19 | −176.8 (4) |
O1—C1—C5—C4 | 76.7 (8) | C16—C17—C18—C19 | 4.3 (7) |
C7—N1—C6—O2 | 0.3 (15) | C17—C18—C19—C20 | −1.6 (7) |
C7—N1—C6—O1 | 179.3 (7) | C17—C18—C19—C22 | −179.4 (5) |
C1—O1—C6—O2 | 0.8 (13) | C18—C19—C20—C21 | −1.6 (8) |
C1—O1—C6—N1 | −178.3 (7) | C22—C19—C20—C21 | 176.4 (5) |
C6—N1—C7—C8 | 150.6 (7) | C19—C20—C21—C16 | 2.2 (9) |
C6—N1—C7—C12 | −33.4 (12) | C17—C16—C21—C20 | 0.3 (8) |
C12—C7—C8—C9 | 1.7 (9) | C15—C16—C21—C20 | 176.7 (5) |
N1—C7—C8—C9 | 177.8 (6) | S1—N3—C22—O4 | −0.4 (6) |
C7—C8—C9—C10 | −0.3 (8) | S1—N3—C22—C19 | 176.5 (4) |
C7—C8—C9—C13 | 179.0 (6) | C20—C19—C22—O4 | 19.0 (7) |
C14—N2—C10—C11 | 179.9 (6) | C18—C19—C22—O4 | −163.1 (5) |
C31—N2—C10—C11 | 10.6 (10) | C20—C19—C22—N3 | −157.9 (4) |
C14—N2—C10—C9 | −1.7 (6) | C18—C19—C22—N3 | 20.0 (7) |
C31—N2—C10—C9 | −171.0 (6) | O6—S1—C23—C24 | −5.1 (5) |
C8—C9—C10—N2 | −179.7 (5) | O5—S1—C23—C24 | −136.2 (5) |
C13—C9—C10—N2 | 0.8 (6) | N3—S1—C23—C24 | 112.1 (5) |
C8—C9—C10—C11 | −1.1 (8) | O6—S1—C23—C28 | 171.6 (5) |
C13—C9—C10—C11 | 179.4 (5) | O5—S1—C23—C28 | 40.5 (5) |
N2—C10—C11—C12 | 179.2 (6) | N3—S1—C23—C28 | −71.2 (5) |
C9—C10—C11—C12 | 1.0 (9) | C28—C23—C24—C25 | −0.7 (9) |
C10—C11—C12—C7 | 0.4 (10) | S1—C23—C24—C25 | 176.0 (6) |
C8—C7—C12—C11 | −1.8 (10) | C23—C24—C25—C26 | 0.8 (11) |
N1—C7—C12—C11 | −177.8 (6) | C24—C25—C26—C27 | 0.1 (12) |
C8—C9—C13—C14 | −179.0 (6) | C25—C26—C27—C28 | −1.1 (11) |
C10—C9—C13—C14 | 0.3 (6) | C26—C27—C28—C23 | 1.1 (9) |
C8—C9—C13—C15 | −3.4 (10) | C26—C27—C28—C29 | −178.9 (6) |
C10—C9—C13—C15 | 175.9 (5) | C24—C23—C28—C27 | −0.2 (8) |
C9—C13—C14—N2 | −1.4 (6) | S1—C23—C28—C27 | −176.8 (4) |
C15—C13—C14—N2 | −177.1 (5) | C24—C23—C28—C29 | 179.8 (6) |
C10—N2—C14—C13 | 1.9 (7) | S1—C23—C28—C29 | 3.2 (7) |
C31—N2—C14—C13 | 171.4 (6) | | |
(III) 4-(5-cyclopentyloxycarbonylamino-1-methylindol- 3-ylmethyl)-3-methoxy-
N-(
o-tolylsulfonyl)benzamide ethanol solvate
top
Crystal data top
C31H33N3O6S·C2H6O | F(000) = 1320 |
Mr = 621.73 | Dx = 1.263 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: C -2yc | Cell parameters from 9728 reflections |
a = 17.216 (3) Å | θ = 2.2–27.8° |
b = 11.033 (2) Å | µ = 0.15 mm−1 |
c = 18.258 (4) Å | T = 293 K |
β = 109.47 (3)° | Prism, colourless |
V = 3269.7 (11) Å3 | 0.40 × 0.30 × 0.15 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1030 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.076 |
Graphite monochromator | θmax = 25.1°, θmin = 2.2° |
Detector resolution: 95 pixels mm-1 | h = 0→20 |
ϕ scans | k = 0→13 |
9728 measured reflections | l = −21→19 |
2726 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max = 0.046 |
2724 reflections | Δρmax = 0.17 e Å−3 |
405 parameters | Δρmin = −0.11 e Å−3 |
5 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: 0.0027 (5) |
Crystal data top
C31H33N3O6S·C2H6O | V = 3269.7 (11) Å3 |
Mr = 621.73 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 17.216 (3) Å | µ = 0.15 mm−1 |
b = 11.033 (2) Å | T = 293 K |
c = 18.258 (4) Å | 0.40 × 0.30 × 0.15 mm |
β = 109.47 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1030 reflections with I > 2σ(I) |
9728 measured reflections | Rint = 0.076 |
2726 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 5 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | Δρmax = 0.17 e Å−3 |
2724 reflections | Δρmin = −0.11 e Å−3 |
405 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.31102 (15) | 0.6437 (2) | 0.30407 (14) | 0.1028 (9) | |
O1 | 0.5547 (4) | −0.4791 (7) | 0.3033 (5) | 0.149 (3) | |
O2 | 0.6602 (5) | −0.3638 (6) | 0.2915 (4) | 0.147 (3) | |
O3 | 0.3675 (3) | 0.0590 (4) | 0.2032 (3) | 0.0921 (16) | |
O4 | 0.3473 (3) | 0.6024 (5) | 0.1631 (3) | 0.1033 (18) | |
O5 | 0.3823 (4) | 0.7170 (5) | 0.3102 (4) | 0.135 (3) | |
O6 | 0.2946 (4) | 0.6085 (6) | 0.3726 (4) | 0.134 (2) | |
N1 | 0.5294 (5) | −0.3403 (7) | 0.2114 (6) | 0.126 (3) | |
H41 | 0.4802 | −0.3675 | 0.2024 | 0.151* | |
N2 | 0.5412 (5) | 0.0235 (8) | 0.0104 (5) | 0.103 (2) | |
N3 | 0.3201 (4) | 0.5115 (5) | 0.2630 (4) | 0.0825 (18) | |
H42 | 0.3136 | 0.4450 | 0.2849 | 0.099* | |
C1 | 0.6160 (10) | −0.552 (2) | 0.3670 (8) | 0.197 (8) | |
H1 | 0.6728 | −0.5525 | 0.3667 | 0.236* | |
C2 | 0.6004 (9) | −0.4787 (15) | 0.4275 (13) | 0.203 (8) | |
H2A | 0.6516 | −0.4658 | 0.4699 | 0.243* | |
H2B | 0.5788 | −0.4002 | 0.4064 | 0.243* | |
C3 | 0.5413 (12) | −0.5406 (14) | 0.4562 (7) | 0.199 (6) | |
H3A | 0.5652 | −0.5554 | 0.5116 | 0.239* | |
H3B | 0.4922 | −0.4915 | 0.4470 | 0.239* | |
C4 | 0.5207 (10) | −0.6550 (14) | 0.4141 (8) | 0.187 (6) | |
H4A | 0.5220 | −0.7208 | 0.4497 | 0.224* | |
H4B | 0.4660 | −0.6510 | 0.3757 | 0.224* | |
C5 | 0.5809 (12) | −0.6745 (13) | 0.3771 (13) | 0.224 (9) | |
H5A | 0.5557 | −0.7128 | 0.3269 | 0.269* | |
H5B | 0.6244 | −0.7269 | 0.4087 | 0.269* | |
C6 | 0.5894 (9) | −0.3915 (12) | 0.2722 (7) | 0.124 (4) | |
C7 | 0.5386 (6) | −0.2468 (8) | 0.1608 (5) | 0.095 (3) | |
C8 | 0.4731 (5) | −0.1673 (7) | 0.1343 (5) | 0.089 (2) | |
H8 | 0.4283 | −0.1727 | 0.1518 | 0.107* | |
C9 | 0.4759 (5) | −0.0790 (8) | 0.0808 (5) | 0.083 (2) | |
C10 | 0.5505 (7) | −0.0725 (9) | 0.0626 (5) | 0.096 (3) | |
C11 | 0.6167 (5) | −0.1493 (11) | 0.0933 (6) | 0.109 (3) | |
H11 | 0.6648 | −0.1402 | 0.0813 | 0.131* | |
C12 | 0.6090 (6) | −0.2408 (9) | 0.1428 (6) | 0.111 (3) | |
H12 | 0.6511 | −0.2967 | 0.1631 | 0.133* | |
C13 | 0.4237 (5) | 0.0177 (8) | 0.0390 (5) | 0.083 (2) | |
C14 | 0.4650 (7) | 0.0741 (8) | −0.0030 (5) | 0.104 (3) | |
H14 | 0.4442 | 0.1387 | −0.0365 | 0.125* | |
C15 | 0.3386 (4) | 0.0454 (7) | 0.0444 (4) | 0.085 (2) | |
H15A | 0.2985 | 0.0491 | −0.0075 | 0.102* | |
H15B | 0.3226 | −0.0194 | 0.0723 | 0.102* | |
C16 | 0.3386 (4) | 0.1635 (7) | 0.0853 (5) | 0.070 (2) | |
C17 | 0.3530 (4) | 0.1679 (8) | 0.1657 (5) | 0.075 (2) | |
C18 | 0.3502 (5) | 0.2788 (9) | 0.2031 (4) | 0.081 (2) | |
H18 | 0.3546 | 0.2810 | 0.2553 | 0.098* | |
C19 | 0.3406 (4) | 0.3837 (7) | 0.1602 (5) | 0.069 (2) | |
C20 | 0.3307 (5) | 0.3817 (8) | 0.0827 (5) | 0.081 (2) | |
H20 | 0.3258 | 0.4533 | 0.0546 | 0.097* | |
C21 | 0.3280 (5) | 0.2700 (10) | 0.0471 (4) | 0.090 (2) | |
H21 | 0.3184 | 0.2686 | −0.0061 | 0.108* | |
C22 | 0.3382 (4) | 0.5068 (9) | 0.1924 (5) | 0.080 (2) | |
C23 | 0.2224 (5) | 0.7141 (8) | 0.2369 (5) | 0.086 (2) | |
C24 | 0.2367 (7) | 0.8167 (8) | 0.2020 (6) | 0.112 (3) | |
H24 | 0.2902 | 0.8448 | 0.2119 | 0.135* | |
C25 | 0.1693 (9) | 0.8796 (9) | 0.1505 (7) | 0.131 (4) | |
H25 | 0.1771 | 0.9507 | 0.1265 | 0.158* | |
C26 | 0.0927 (8) | 0.8336 (12) | 0.1370 (6) | 0.135 (4) | |
H26 | 0.0475 | 0.8726 | 0.1022 | 0.162* | |
C27 | 0.0808 (7) | 0.7309 (12) | 0.1736 (7) | 0.117 (3) | |
H27 | 0.0272 | 0.7041 | 0.1641 | 0.140* | |
C28 | 0.1451 (6) | 0.6641 (9) | 0.2246 (5) | 0.101 (3) | |
C29 | 0.1247 (6) | 0.5544 (7) | 0.2630 (5) | 0.110 (3) | |
H29A | 0.0676 | 0.5342 | 0.2385 | 0.165* | |
H29B | 0.1350 | 0.5712 | 0.3170 | 0.165* | |
H29C | 0.1583 | 0.4876 | 0.2581 | 0.165* | |
C30 | 0.3844 (6) | 0.0602 (7) | 0.2850 (5) | 0.118 (3) | |
H30A | 0.4057 | −0.0172 | 0.3063 | 0.178* | |
H30B | 0.3345 | 0.0768 | 0.2958 | 0.178* | |
H30C | 0.4243 | 0.1220 | 0.3081 | 0.178* | |
C31 | 0.6015 (7) | 0.0723 (10) | −0.0228 (7) | 0.155 (4) | |
H31A | 0.6380 | 0.0087 | −0.0268 | 0.232* | |
H31B | 0.6328 | 0.1354 | 0.0102 | 0.232* | |
H31C | 0.5732 | 0.1047 | −0.0735 | 0.232* | |
O7 | 0.7769 (4) | −0.1859 (5) | 0.3392 (4) | 0.1110 (19) | |
H43 | 0.742 (4) | −0.239 (6) | 0.323 (5) | 0.133* | |
C32 | 0.7948 (9) | −0.2447 (13) | 0.4707 (8) | 0.208 (6) | |
H32A | 0.8147 | −0.2098 | 0.5218 | 0.313* | |
H32B | 0.8324 | −0.3063 | 0.4664 | 0.313* | |
H32C | 0.7415 | −0.2799 | 0.4620 | 0.313* | |
C33 | 0.7889 (14) | −0.1547 (15) | 0.4155 (7) | 0.291 (12) | |
H33A | 0.7440 | −0.1016 | 0.4154 | 0.350* | |
H33B | 0.8390 | −0.1069 | 0.4336 | 0.350* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.1034 (19) | 0.0887 (17) | 0.105 (2) | −0.0110 (15) | 0.0201 (15) | −0.0229 (15) |
O1 | 0.107 (5) | 0.147 (6) | 0.173 (7) | −0.019 (5) | 0.018 (5) | 0.043 (5) |
O2 | 0.080 (4) | 0.158 (6) | 0.175 (7) | −0.029 (5) | 0.007 (5) | 0.005 (5) |
O3 | 0.126 (5) | 0.056 (3) | 0.095 (4) | −0.008 (3) | 0.038 (3) | 0.007 (3) |
O4 | 0.108 (4) | 0.080 (4) | 0.135 (5) | −0.009 (3) | 0.058 (4) | 0.026 (4) |
O5 | 0.092 (5) | 0.083 (4) | 0.199 (7) | −0.032 (3) | 0.005 (4) | −0.024 (4) |
O6 | 0.185 (7) | 0.120 (5) | 0.095 (4) | −0.013 (4) | 0.046 (4) | −0.025 (4) |
N1 | 0.079 (6) | 0.102 (6) | 0.196 (9) | −0.017 (4) | 0.044 (6) | 0.028 (6) |
N2 | 0.098 (6) | 0.114 (6) | 0.114 (6) | −0.032 (5) | 0.058 (5) | −0.040 (5) |
N3 | 0.096 (5) | 0.054 (4) | 0.101 (5) | −0.008 (3) | 0.039 (4) | −0.004 (3) |
C1 | 0.144 (13) | 0.32 (3) | 0.112 (10) | 0.078 (15) | 0.025 (9) | 0.081 (13) |
C2 | 0.121 (11) | 0.187 (16) | 0.27 (2) | −0.037 (10) | 0.026 (12) | 0.080 (16) |
C3 | 0.282 (19) | 0.171 (13) | 0.136 (10) | −0.030 (13) | 0.060 (11) | −0.048 (10) |
C4 | 0.236 (17) | 0.180 (14) | 0.121 (9) | −0.075 (12) | 0.029 (10) | −0.012 (9) |
C5 | 0.32 (2) | 0.108 (13) | 0.32 (2) | 0.040 (12) | 0.199 (19) | 0.015 (12) |
C6 | 0.097 (9) | 0.131 (10) | 0.140 (10) | 0.008 (9) | 0.034 (8) | 0.007 (8) |
C7 | 0.063 (6) | 0.090 (7) | 0.127 (7) | −0.014 (5) | 0.026 (6) | 0.006 (6) |
C8 | 0.082 (6) | 0.090 (6) | 0.096 (6) | −0.003 (6) | 0.031 (5) | 0.003 (5) |
C9 | 0.077 (6) | 0.095 (7) | 0.088 (6) | −0.007 (5) | 0.043 (5) | −0.014 (5) |
C10 | 0.122 (10) | 0.089 (7) | 0.096 (7) | −0.020 (6) | 0.061 (6) | 0.004 (5) |
C11 | 0.064 (6) | 0.122 (8) | 0.140 (8) | −0.016 (7) | 0.033 (6) | −0.051 (7) |
C12 | 0.070 (7) | 0.093 (7) | 0.172 (9) | −0.010 (5) | 0.044 (6) | −0.003 (7) |
C13 | 0.077 (6) | 0.085 (6) | 0.097 (6) | −0.002 (5) | 0.041 (5) | −0.011 (5) |
C14 | 0.113 (8) | 0.094 (6) | 0.107 (7) | −0.008 (6) | 0.042 (6) | 0.000 (5) |
C15 | 0.076 (6) | 0.089 (6) | 0.082 (5) | −0.001 (4) | 0.017 (4) | −0.023 (4) |
C16 | 0.079 (5) | 0.059 (5) | 0.067 (6) | 0.005 (4) | 0.018 (4) | 0.007 (5) |
C17 | 0.065 (5) | 0.076 (6) | 0.088 (6) | 0.003 (4) | 0.029 (4) | 0.009 (6) |
C18 | 0.082 (6) | 0.088 (6) | 0.078 (6) | −0.013 (5) | 0.031 (4) | 0.000 (6) |
C19 | 0.063 (5) | 0.056 (6) | 0.097 (7) | −0.001 (4) | 0.040 (4) | 0.010 (5) |
C20 | 0.093 (6) | 0.088 (7) | 0.066 (6) | −0.003 (4) | 0.033 (4) | 0.025 (5) |
C21 | 0.092 (6) | 0.106 (7) | 0.075 (5) | 0.002 (5) | 0.031 (4) | −0.008 (6) |
C22 | 0.073 (6) | 0.078 (7) | 0.098 (7) | −0.003 (4) | 0.040 (5) | −0.001 (5) |
C23 | 0.086 (7) | 0.070 (6) | 0.097 (6) | −0.004 (5) | 0.024 (5) | −0.022 (5) |
C24 | 0.143 (9) | 0.069 (6) | 0.128 (8) | −0.011 (6) | 0.049 (8) | −0.008 (6) |
C25 | 0.124 (10) | 0.113 (8) | 0.147 (9) | −0.002 (8) | 0.032 (7) | 0.027 (7) |
C26 | 0.102 (10) | 0.124 (9) | 0.148 (10) | 0.014 (7) | 0.000 (7) | 0.020 (8) |
C27 | 0.092 (8) | 0.117 (8) | 0.154 (10) | −0.009 (7) | 0.058 (8) | −0.021 (7) |
C28 | 0.077 (7) | 0.112 (8) | 0.116 (7) | −0.023 (7) | 0.035 (6) | −0.024 (6) |
C29 | 0.129 (8) | 0.080 (6) | 0.129 (8) | −0.037 (5) | 0.052 (6) | −0.028 (6) |
C30 | 0.174 (9) | 0.097 (7) | 0.076 (7) | −0.019 (6) | 0.031 (6) | 0.011 (5) |
C31 | 0.142 (9) | 0.158 (10) | 0.212 (11) | −0.029 (8) | 0.123 (8) | 0.001 (8) |
O7 | 0.142 (5) | 0.113 (5) | 0.085 (4) | −0.028 (4) | 0.046 (4) | −0.008 (4) |
C32 | 0.210 (14) | 0.186 (12) | 0.178 (13) | −0.051 (10) | −0.003 (11) | 0.029 (10) |
C33 | 0.46 (3) | 0.30 (3) | 0.139 (14) | −0.09 (2) | 0.134 (17) | 0.028 (15) |
Geometric parameters (Å, º) top
S1—O6 | 1.426 (7) | C13—C15 | 1.531 (10) |
S1—O5 | 1.443 (6) | C14—H14 | 0.9300 |
S1—N3 | 1.671 (6) | C15—C16 | 1.502 (9) |
S1—C23 | 1.785 (9) | C15—H15A | 0.9700 |
O1—C6 | 1.357 (12) | C15—H15B | 0.9700 |
O1—C1 | 1.517 (15) | C16—C21 | 1.348 (10) |
O2—C6 | 1.189 (13) | C16—C17 | 1.406 (9) |
O3—C17 | 1.365 (8) | C17—C18 | 1.409 (10) |
O3—C30 | 1.423 (9) | C18—C19 | 1.376 (9) |
O4—C22 | 1.216 (8) | C18—H18 | 0.9300 |
N1—C6 | 1.362 (12) | C19—C20 | 1.369 (9) |
N1—C7 | 1.429 (11) | C19—C22 | 1.486 (10) |
N1—H41 | 0.8600 | C20—C21 | 1.386 (10) |
N2—C14 | 1.370 (10) | C20—H20 | 0.9300 |
N2—C10 | 1.397 (10) | C21—H21 | 0.9300 |
N2—C31 | 1.469 (10) | C23—C24 | 1.362 (10) |
N3—C22 | 1.424 (9) | C23—C28 | 1.388 (11) |
N3—H42 | 0.8600 | C24—C25 | 1.409 (12) |
C1—C2 | 1.466 (19) | C24—H24 | 0.9300 |
C1—C5 | 1.51 (2) | C25—C26 | 1.357 (13) |
C1—H1 | 0.9800 | C25—H25 | 0.9300 |
C2—C3 | 1.461 (17) | C26—C27 | 1.365 (13) |
C2—H2A | 0.9700 | C26—H26 | 0.9300 |
C2—H2B | 0.9700 | C27—C28 | 1.396 (12) |
C3—C4 | 1.458 (15) | C27—H27 | 0.9300 |
C3—H3A | 0.9700 | C28—C29 | 1.498 (11) |
C3—H3B | 0.9700 | C29—H29A | 0.9600 |
C4—C5 | 1.430 (18) | C29—H29B | 0.9600 |
C4—H4A | 0.9700 | C29—H29C | 0.9600 |
C4—H4B | 0.9700 | C30—H30A | 0.9600 |
C5—H5A | 0.9700 | C30—H30B | 0.9600 |
C5—H5B | 0.9700 | C30—H30C | 0.9600 |
C7—C12 | 1.359 (12) | C31—H31A | 0.9600 |
C7—C8 | 1.382 (10) | C31—H31B | 0.9600 |
C8—C9 | 1.393 (10) | C31—H31C | 0.9600 |
C8—H8 | 0.9300 | O7—C33 | 1.39 (2) |
C9—C10 | 1.432 (11) | O7—H43 | 0.82 (7) |
C9—C13 | 1.438 (11) | C32—C33 | 1.395 (9) |
C10—C11 | 1.381 (12) | C32—H32A | 0.9600 |
C11—C12 | 1.389 (13) | C32—H32B | 0.9600 |
C11—H11 | 0.9300 | C32—H32C | 0.9600 |
C12—H12 | 0.9300 | C33—H33A | 0.9700 |
C13—C14 | 1.357 (11) | C33—H33B | 0.9700 |
| | | |
O6—S1—O5 | 119.8 (4) | C16—C15—H15A | 109.3 |
O6—S1—N3 | 103.4 (4) | C13—C15—H15A | 109.3 |
O5—S1—N3 | 108.7 (4) | C16—C15—H15B | 109.3 |
O6—S1—C23 | 110.3 (4) | C13—C15—H15B | 109.3 |
O5—S1—C23 | 108.6 (4) | H15A—C15—H15B | 108.0 |
N3—S1—C23 | 104.9 (3) | C21—C16—C17 | 117.2 (8) |
C6—O1—C1 | 114.1 (11) | C21—C16—C15 | 121.4 (8) |
C17—O3—C30 | 117.2 (6) | C17—C16—C15 | 121.4 (8) |
C6—N1—C7 | 127.5 (10) | O3—C17—C16 | 115.6 (8) |
C6—N1—H41 | 116.3 | O3—C17—C18 | 123.5 (8) |
C7—N1—H41 | 116.3 | C16—C17—C18 | 120.9 (8) |
C14—N2—C10 | 108.4 (8) | C19—C18—C17 | 118.1 (7) |
C14—N2—C31 | 122.9 (10) | C19—C18—H18 | 121.0 |
C10—N2—C31 | 128.5 (10) | C17—C18—H18 | 121.0 |
C22—N3—S1 | 121.3 (6) | C20—C19—C18 | 121.7 (7) |
C22—N3—H42 | 119.4 | C20—C19—C22 | 114.4 (8) |
S1—N3—H42 | 119.4 | C18—C19—C22 | 123.9 (8) |
C2—C1—C5 | 102.8 (14) | C19—C20—C21 | 118.2 (7) |
C2—C1—O1 | 91.6 (15) | C19—C20—H20 | 120.9 |
C5—C1—O1 | 111.4 (14) | C21—C20—H20 | 120.9 |
C2—C1—H1 | 116.0 | C16—C21—C20 | 123.7 (7) |
C5—C1—H1 | 116.0 | C16—C21—H21 | 118.1 |
O1—C1—H1 | 116.0 | C20—C21—H21 | 118.1 |
C3—C2—C1 | 109.6 (15) | O4—C22—N3 | 117.8 (8) |
C3—C2—H2A | 109.7 | O4—C22—C19 | 126.5 (9) |
C1—C2—H2A | 109.7 | N3—C22—C19 | 115.7 (8) |
C3—C2—H2B | 109.8 | C24—C23—C28 | 124.6 (9) |
C1—C2—H2B | 109.8 | C24—C23—S1 | 115.9 (8) |
H2A—C2—H2B | 108.2 | C28—C23—S1 | 119.5 (8) |
C4—C3—C2 | 106.9 (13) | C23—C24—C25 | 119.0 (10) |
C4—C3—H3A | 110.3 | C23—C24—H24 | 120.5 |
C2—C3—H3A | 110.3 | C25—C24—H24 | 120.5 |
C4—C3—H3B | 110.3 | C26—C25—C24 | 118.1 (11) |
C2—C3—H3B | 110.3 | C26—C25—H25 | 120.9 |
H3A—C3—H3B | 108.6 | C24—C25—H25 | 120.9 |
C5—C4—C3 | 107.0 (14) | C25—C26—C27 | 121.1 (10) |
C5—C4—H4A | 110.3 | C25—C26—H26 | 119.5 |
C3—C4—H4A | 110.3 | C27—C26—H26 | 119.5 |
C5—C4—H4B | 110.3 | C26—C27—C28 | 123.4 (10) |
C3—C4—H4B | 110.3 | C26—C27—H27 | 118.3 |
H4A—C4—H4B | 108.6 | C28—C27—H27 | 118.3 |
C4—C5—C1 | 107.8 (14) | C23—C28—C27 | 113.7 (9) |
C4—C5—H5A | 110.2 | C23—C28—C29 | 127.4 (10) |
C1—C5—H5A | 110.2 | C27—C28—C29 | 118.8 (9) |
C4—C5—H5B | 110.2 | C28—C29—H29A | 109.5 |
C1—C5—H5B | 110.2 | C28—C29—H29B | 109.5 |
H5A—C5—H5B | 108.5 | H29A—C29—H29B | 109.5 |
O2—C6—O1 | 127.6 (12) | C28—C29—H29C | 109.5 |
O2—C6—N1 | 124.0 (13) | H29A—C29—H29C | 109.5 |
O1—C6—N1 | 108.4 (12) | H29B—C29—H29C | 109.5 |
C12—C7—C8 | 125.0 (9) | O3—C30—H30A | 109.5 |
C12—C7—N1 | 119.5 (9) | O3—C30—H30B | 109.5 |
C8—C7—N1 | 115.5 (9) | H30A—C30—H30B | 109.5 |
C7—C8—C9 | 118.3 (9) | O3—C30—H30C | 109.5 |
C7—C8—H8 | 120.8 | H30A—C30—H30C | 109.5 |
C9—C8—H8 | 120.8 | H30B—C30—H30C | 109.5 |
C8—C9—C10 | 116.2 (9) | N2—C31—H31A | 109.5 |
C8—C9—C13 | 136.8 (9) | N2—C31—H31B | 109.5 |
C10—C9—C13 | 106.9 (9) | H31A—C31—H31B | 109.5 |
C11—C10—N2 | 129.4 (11) | N2—C31—H31C | 109.5 |
C11—C10—C9 | 123.9 (9) | H31A—C31—H31C | 109.5 |
N2—C10—C9 | 106.7 (9) | H31B—C31—H31C | 109.5 |
C10—C11—C12 | 117.7 (10) | C33—O7—H43 | 112 (7) |
C10—C11—H11 | 121.1 | C33—C32—H32A | 109.5 |
C12—C11—H11 | 121.1 | C33—C32—H32B | 109.4 |
C7—C12—C11 | 118.7 (10) | H32A—C32—H32B | 109.5 |
C7—C12—H12 | 120.7 | C33—C32—H32C | 109.5 |
C11—C12—H12 | 120.7 | H32A—C32—H32C | 109.5 |
C14—C13—C9 | 106.7 (8) | H32B—C32—H32C | 109.5 |
C14—C13—C15 | 129.5 (9) | O7—C33—C32 | 120.1 (14) |
C9—C13—C15 | 123.8 (8) | O7—C33—H33A | 107.3 |
C13—C14—N2 | 111.3 (8) | C32—C33—H33A | 107.2 |
C13—C14—H14 | 124.4 | O7—C33—H33B | 107.3 |
N2—C14—H14 | 124.4 | C32—C33—H33B | 107.3 |
C16—C15—C13 | 111.4 (6) | H33A—C33—H33B | 106.9 |
| | | |
O6—S1—N3—C22 | −179.0 (5) | C14—C13—C15—C16 | −68.7 (10) |
O5—S1—N3—C22 | −50.7 (6) | C9—C13—C15—C16 | 111.3 (8) |
C23—S1—N3—C22 | 65.4 (6) | C13—C15—C16—C21 | 84.1 (9) |
C6—O1—C1—C2 | 97.9 (13) | C13—C15—C16—C17 | −93.1 (8) |
C6—O1—C1—C5 | −157.7 (13) | C30—O3—C17—C16 | 178.5 (7) |
C5—C1—C2—C3 | −14.7 (17) | C30—O3—C17—C18 | −3.1 (10) |
O1—C1—C2—C3 | 97.6 (15) | C21—C16—C17—O3 | −176.8 (7) |
C1—C2—C3—C4 | 1.0 (18) | C15—C16—C17—O3 | 0.5 (9) |
C2—C3—C4—C5 | 14.3 (19) | C21—C16—C17—C18 | 4.7 (10) |
C3—C4—C5—C1 | −24 (2) | C15—C16—C17—C18 | −177.9 (7) |
C2—C1—C5—C4 | 23.7 (18) | O3—C17—C18—C19 | 175.6 (6) |
O1—C1—C5—C4 | −73 (2) | C16—C17—C18—C19 | −6.0 (10) |
C1—O1—C6—O2 | −3.4 (18) | C17—C18—C19—C20 | 2.7 (10) |
C1—O1—C6—N1 | 174.4 (11) | C17—C18—C19—C22 | −178.8 (6) |
C7—N1—C6—O2 | −0.4 (19) | C18—C19—C20—C21 | 1.8 (10) |
C7—N1—C6—O1 | −178.3 (8) | C22—C19—C20—C21 | −176.9 (7) |
C6—N1—C7—C12 | 33.3 (15) | C17—C16—C21—C20 | 0.0 (11) |
C6—N1—C7—C8 | −146.2 (10) | C15—C16—C21—C20 | −177.4 (7) |
C12—C7—C8—C9 | 4.8 (12) | C19—C20—C21—C16 | −3.2 (11) |
N1—C7—C8—C9 | −175.8 (7) | S1—N3—C22—O4 | 0.3 (9) |
C7—C8—C9—C10 | −4.9 (10) | S1—N3—C22—C19 | −177.2 (5) |
C7—C8—C9—C13 | 179.5 (8) | C20—C19—C22—O4 | −17.9 (10) |
C14—N2—C10—C11 | −179.6 (8) | C18—C19—C22—O4 | 163.4 (7) |
C31—N2—C10—C11 | −3.4 (14) | C20—C19—C22—N3 | 159.3 (6) |
C14—N2—C10—C9 | 0.1 (8) | C18—C19—C22—N3 | −19.3 (10) |
C31—N2—C10—C9 | 176.3 (8) | O6—S1—C23—C24 | 135.9 (6) |
C8—C9—C10—C11 | 1.6 (12) | O5—S1—C23—C24 | 2.8 (7) |
C13—C9—C10—C11 | 178.5 (8) | N3—S1—C23—C24 | −113.3 (6) |
C8—C9—C10—N2 | −178.1 (6) | O6—S1—C23—C28 | −43.0 (7) |
C13—C9—C10—N2 | −1.3 (8) | O5—S1—C23—C28 | −176.2 (6) |
N2—C10—C11—C12 | −178.0 (8) | N3—S1—C23—C28 | 67.7 (7) |
C9—C10—C11—C12 | 2.3 (13) | C28—C23—C24—C25 | 1.3 (13) |
C8—C7—C12—C11 | −0.8 (14) | S1—C23—C24—C25 | −177.6 (7) |
N1—C7—C12—C11 | 179.8 (8) | C23—C24—C25—C26 | −1.2 (14) |
C10—C11—C12—C7 | −2.7 (13) | C24—C25—C26—C27 | 1.7 (17) |
C8—C9—C13—C14 | 177.8 (9) | C25—C26—C27—C28 | −2.3 (18) |
C10—C9—C13—C14 | 1.9 (8) | C24—C23—C28—C27 | −1.7 (12) |
C8—C9—C13—C15 | −2.1 (13) | S1—C23—C28—C27 | 177.2 (7) |
C10—C9—C13—C15 | −178.0 (6) | C24—C23—C28—C29 | −177.7 (8) |
C9—C13—C14—N2 | −1.9 (9) | S1—C23—C28—C29 | 1.2 (11) |
C15—C13—C14—N2 | 178.0 (7) | C26—C27—C28—C23 | 2.2 (14) |
C10—N2—C14—C13 | 1.2 (9) | C26—C27—C28—C29 | 178.5 (10) |
C31—N2—C14—C13 | −175.3 (7) | | |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C31H33N3O6S·H2O | C31H33N3O6S·CH4O | C31H33N3O6S·C2H6O |
Mr | 593.68 | 607.71 | 621.73 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, Cc | Monoclinic, Cc |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 9.983 (2), 31.580 (6), 10.192 (2) | 17.002 (3), 11.111 (2), 17.129 (3) | 17.216 (3), 11.033 (2), 18.258 (4) |
α, β, γ (°) | 90, 111.55 (3), 90 | 90, 105.94 (2), 90 | 90, 109.47 (3), 90 |
V (Å3) | 2988.6 (12) | 3111.4 (10) | 3269.7 (11) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.16 | 0.16 | 0.15 |
Crystal size (mm) | 0.34 × 0.26 × 0.16 | 0.39 × 0.33 × 0.03 | 0.40 × 0.30 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16987, 5087, 2909 | 2839, 2839, 1811 | 9728, 2726, 1030 |
Rint | 0.080 | 0.000 | 0.076 |
(sin θ/λ)max (Å−1) | 0.596 | 0.604 | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.192, 1.03 | 0.048, 0.138, 1.01 | 0.050, 0.114, 0.81 |
No. of reflections | 5087 | 2839 | 2724 |
No. of parameters | 391 | 396 | 405 |
No. of restraints | 0 | 2 | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.41 | 0.29, −0.17 | 0.17, −0.11 |
Selected torsion angles (°) for the solvates of zafirlukast, (I)-(III) [the torsion angles for (II) are taken from a mirror symmetry-related molecule for comparison reasons]. top | (I) | (II) | (III) | Calculated |
C14-C13-C15-C16 | 66.2 (4) | 65.3 (7) | 68.7 (10) | 67.8 |
C13-C15-C16-C21 | -81.3 (4) | -85.9 (6) | -84.1 (9) | -83.4 |
C22-N3-S1-C23 | -61.8 (3) | -63.7 (4) | -65.4 (6) | -58.7 |
N3-S1-C23-C28 | -66.4 (3) | -71.2 (5) | -67.7 (7) | -64.1 |
O2-C6-O1-C1 | -5.4 (6) | 0.8 (13) | 3.4 (18) | 3.9 |
C1-C2-C3-C4 | -16.9 (6) | -14.6 (11) | -1.0 (18) | -21.0 |
C2-C3-C4-C5 | -0.8 (7) | -6.0 (9) | 14.3 (19) | -2.8 |
C3-C4-C5-C1 | 18.9 (6) | 22.3 (8) | 23.7 (18) | 25.6 |
C4-C5-C1-C2 | -28.9 (5) | -32.1 (10) | -24 (2) | -38.5 |
C5-C1-C2-C3 | 28.5 (5) | 28.6 (12) | 14.7 (17) | 36.8 |
Comparison of hydrogen-bond geometry in the solvates of zafirlukas (Å, °) topD—H···A | D—H | H···A | D···A | D—H···A | symmetry code |
(I) | | | | | |
N1-H41···O4 | 0.86 | 2.133 | 2.984 (4) | 170 | x − 1,y,z − 1 |
N3-H42···O7 | 0.86 | 1.992 | 2.828 (4) | 164 | |
O7-H7A···O2 | 0.90 (4) | 1.904 (4) | 2.792 (4) | 170 (4) | x + 1,y,z |
O7-H7B···O6 | 0.88 (5) | 2.042 (5) | 2.904 (4) | 168 (5) | 2 − x,-y,2 − z |
| | | | | |
(II) | | | | | |
N1-H41···O4 | 0.86 | 2.163 | 3.008 (7) | 168 | x,y + 1,z |
N3-H42···O7 | 0.86 | 1.992 | 2.829 (8) | 164 | |
O7-H43····O2 | 0.805 (9) | 1.94 (9) | 2.731 (8) | 169 (9) | x + 1/2,y − 1/2,z |
| | | | | |
(III) | | | | | |
N1-H41···O4 | 0.86 | 2.190 | 3.03 (1) | 167 | x,y − 1,z |
N3-H42···O7 | 0.86 | 1.977 | 2.81 (1) | 166 | x − 1/2,y + 1/2,z |
O7-H43···O2 | 0.821 (9) | 1.92 (9) | 2.74 (1) | 177 (8) | |
Zafirlukast is an effective and safe prophylactic treatment for asthma, its effect remaining evident up to 12 h after drug take-up. Some different phases and derivatives of zafirlukast have been found to possess useful medical and biological activities (Adkins & Brogden, 1998). Zafirlukast can be prepared by methods described by Matassa et al. (1990). The patent (Reference?) discloses three forms of zafirlukast, differing with respect to their physical properties, stability, spectroscopic data and method of preparation; these are designated Forms A, B and X. Form X is a stable crystalline form of zafirlukast, but has relatively poor bioavailability. Form B is an unstable crystalline form of zafirlukast hydrate. The method disclosed in the patent for the preparation of Form B is by precipitation with water from acetone. Because of its unstable nature, this hydrate is difficult to prepare and maintain in a form having a constant and reproducible water content, and is particularly difficult to handle during formulation. Form A is an amorphous form of zafirlukast, prepared by dehydration of Form B in a vacuum oven for up to 24 h at 393 K; typically, the pressure is about 20 mbar (1 bar = 100000 Pa). Form A has relatively good bioavailability. However, under conditions of high relative humidity and elevated temperatures, conversion of form A into form B has been found to occur. Accordingly, it may, in certain circumstances, be desirable to store pharmaceutical formulations of form A in the presence of a suitable desiccant, such as silica gel. It may also be desirable to keep them in an airtight container, such as a blister pack.
The crystal structure of zafirlukast itself is not known. We have crystallized three different solvates of zafirlukast, namely the monohydrate, (I) (US Patent 5993859; Reference?), the methanolate, (II), and the ethanolate, (III), in order to examine the possibility of introducing new drugs and as useful intermediate products for fabrication processes. The three solvates crystallize in the monoclinic crystal system, with (I) in space group P21/n, and (II) and (III) in space group Cc. The molecular structure of zafirlukast, with the atomic labelling, is shown in Fig. 1. \sch
Zafirlukast adopts a Z-shaped conformation in the three crystal structures. Selected torsion angles for the three solvates and for the calculated one zafirlukast itself? (MM+; Allinger & Yuh, 1982) are given in Table 1. The conformation of the cyclopentyl-N-phenylcarbamate moiety in the three solvates may be compared with that of 3-(4-bromobenzoato)cyclopentyl-N-phenylcarbamate [Vigne et al., 1991; refcode PACGIJ in the Cambridge Structural Database (CSD; Allen, 2002)] and (-)-[1R,3S,2(1E)]-3-N-(4-bromophenylcarbamoyloxy)-2-(1-N,N- diisopropylcarbamoyloxymethylidene)cyclopentyl N,N-diisopropylcarbamate (Gralla et al., 2002; CSD refcode PUZBOB]. The conformation may be expressed by the angles between the mean planes formed by the atoms C1, C2 and C5 (P1), O1, O2, N1 and C6 (P2), and C7—C12 (P3). The angles between planes P1 and P2 are in the range 72.0–87.?° in the solvates of zafirlukast, and 74.3 and 60.6° in PACGIJ and PUZBOB, respectively. The angles between planes P2 and P3 in the solvates are in the range 31.3–33.3°, and 27.8 and 13.5° in PACGIJ and PUZBOB, respectively. Finally, the angles between the mean planes P1 and P3 in the solvates are in the range 39.7–75.5°, and 81.5 and 67.5° in PACGIJ and PUZBOB, respectively. It is also important to note the difference in O1—C1 bond length. This bond was found to be 1.441 Å in PUZBOB, as well as in many other cyclopentylcarbamates, while it is significantly longer in PACGIJ (1.522 Å) and in the present solvates of zafirlukast [1.521 (5), 1.521 (11) and 1.517 (15) Å in (I)-(III), respectively. The reason for the lengthening of this bond is not known. As a result of the large atomic displacement parameters of the terminal groups [cyclopentane in all three compounds and a phenyl ring in compound (III)], some bond lengths are too short.
The methanolate, (II), and the ethanolate, (III), are isostructural. The solvent molecules are connected to two zafirlukast molecules through N—H···O—H and C═O···H—O hydrogen bonds (Table 2). The water molecule in the monohydrate, (I), takes part in three hydrogen bonds, thus serving as a connector between three molecules of zafirlukast. These hydrogen bonds are H2O···H—N, HOH···O═C and HOH···O═S (Table 2.). Although the role of the water molecules in (I) differs from that of methanol or ethanol in (II) or (III), the packing of zafirlukast is very similar (Fig. 2). All three structures contain layers of zafirlukast molecules that are exactly comparable. In (I), these lie in the ac plane, while in (II) and (III), they lie in the ab plane. The solvate molecules lie in positions adjacent to these layers, hydrogen bonded to the C═O groups (Table 2). The difference between the structures lies in how the layers are stacked.
In (I), the water molecule has its second O—H bond projecting approximately perpendicular to the plane of the layer. This forms a hydrogen bond to one S═O group in an adjacent layer. Adjacent layers are `flipped' in order to form this hydrogen bond. Stacked along the b direction, the water molecules appear to be `sandwiched' in hydrophilic regions between two layers of zafirlukast molecules. These sandwiches then meet in hydrophobic regions. The flipping of the layer to form the hydrophilic sandwich introduces a centre of symmetry and gives rise to the centrosymmetric space group.
In (II) and (III), a methyl or ethyl group projects perpendicular to the plane of the layer, forming a hydrophobic interface, and the layers stack one on top of the other (along the c direction) without flipping. This gives the polar space group.
From differential scanning calorimeter (DSC) thermographs, it was seen that the solvent release in each of the compounds is either close to or at the melting temperature of the solid material, which is above the boiling points of the pure solvents. This high-temperature release is an indication that the solvents are involved in strong hydrogen bonding. Since the solvent release is so close to the melting temperature it was not possible to measure the enthalpy of release. The measured enthalpies of fusion are 77.96 (6), 80.22 (6), and 55.96 (6) kJ mol−1 for (I), (II), and (III), respectively.
Table 1. Selected torsion angles (°) in the solvates of zafirlukast
Table 2. Comparison of hydrogen-bonding geometry in the solvates of zafirlukast