Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102012544/fg1656sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012544/fg1656IAsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012544/fg1656ICsup3.hkl |
CCDC references: 193455; 193456
Cilostazol, form (IA), was isolated without recrystallization from bulk active pharmaceutical ingredient received from Laboratorios Phoenix, Buenos Aires, Argentina (Lot 1002974001). A colourless needle-like crystal of (I) was isolated from this lot and was found to crystallize in the orthorhombic space group Pbca. Cilostazol, form (IC), was isolated from material recovered after performing heat-cycling experiments using differential scanning calorimetry (Stowell & Whittle, 2002; Stowell et al., 2002). The material used for heat cycling was obtained from Laboratorios Phoenix, Buenos Aires, Argentina (Lot 1002974001). A single colourless plate-like crystal isolated from the resulting heat-cycled material was found to crystallize in the monoclinic space group P21/n.
For (IA), atoms C3 and C4 were disordered with a site-occupancy factor of 0.80, while atoms C3A and C4A had a site-occupancy factor of 0.20. Atoms C3A and C4A were located in difference Fourier maps; however, all parameters were fixed in the final cycles of refinement. H atoms on C3A and C4A were calculated and fixed, with C—H = 1.00 Å and Uiso(H) = 1.3Ueq(C). All other H atoms in both polymorphs were initially located in a difference Fourier map, but were calculated and fixed in the final cycles of refinement to an ideal geometry, with C—H = 1.00 Å and Uiso(H) = 1.3Ueq(C), and N—H = 0.95 Å and Uiso(H) = 1.3Ueq(N).
For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: KappaCCD Server Software; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR (Burla et al., 1989); program(s) used to refine structure: LSFM in OpenMolEN (Nonius, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CIFGEN in OpenMolEN.
C20H27N5O2 | Dx = 1.26 Mg m−3 |
Mr = 369.47 | Melting point: 432 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3849 reflections |
a = 11.324 (1) Å | θ = 1.1–25.4° |
b = 9.855 (1) Å | µ = 0.08 mm−1 |
c = 35.012 (1) Å | T = 294 K |
V = 3907.3 (5) Å3 | Needle, colourless |
Z = 8 | 0.58 × 0.08 × 0.05 mm |
F(000) = 1584 |
95mm CCD camera on κ goniostat diffractometer | 2341 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Horizontally mounted graphite crystal monochromator | θmax = 25.4°, θmin = 2.5° |
Detector resolution: 9 pixels mm-1 | h = 0→13 |
CCD scans | k = 0→11 |
4045 measured reflections | l = −42→0 |
3548 independent reflections |
Refinement on F | 0 constraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.042 | w = 4Fo2/[σ2(Fo2) + 0.0001Fo4] |
wR(F2) = 0.042 | (Δ/σ)max = 0.001 |
S = 2.10 | Δρmax = 0.13 e Å−3 |
2540 reflections | Δρmin = −0.15 e Å−3 |
255 parameters | Extinction correction: isotropic (Zachariasen, 1963), eq. 22, p. 292 in Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291-294. Copenhagen: Munksgaard. |
132 restraints | Extinction coefficient: 1.2770 × 10-06 |
C20H27N5O2 | V = 3907.3 (5) Å3 |
Mr = 369.47 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.324 (1) Å | µ = 0.08 mm−1 |
b = 9.855 (1) Å | T = 294 K |
c = 35.012 (1) Å | 0.58 × 0.08 × 0.05 mm |
95mm CCD camera on κ goniostat diffractometer | 2341 reflections with I > 2σ(I) |
4045 measured reflections | Rint = 0.028 |
3548 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 132 restraints |
wR(F2) = 0.042 | H-atom parameters constrained |
S = 2.10 | Δρmax = 0.13 e Å−3 |
2540 reflections | Δρmin = −0.15 e Å−3 |
255 parameters |
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 distance, 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) treatmemt of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Orthonormal Equation of Plane 1 -0.7333 X + 0.6324 Y + -0.2495 Z - -5.7886 = 0 0.0004 0.0005 0.0006 0.0056 Crystallographic Equation of Plane -8.3040 X + 6.2330 Y + -8.7360 Z - -5.7886 = 0 0.0049 0.0050 0.0216 0.0056 Atom X Y Z Distance Esd C16 7.1994 2.4774 8.3155 0.0011 ± 0.0013 N17 6.3003 1.5783 8.6892 - 0.0014 ± 0.0012 N18 6.0267 0.8313 7.5897 0.0011 ± 0.0012 N19 6.7200 1.2342 6.5794 - 0.0004 ± 0.0011 N20 7.4667 2.2746 7.0223 - 0.0005 ± 0.0010 Chi Squared = 3.4 Orthonormal Equation of Plane 2 0.1931 X + 0.7871 Y + -0.5858 Z - -1.7175 = 0 0.0010 0.0004 0.0007 0.0206 Crystallographic Equation of Plane 2.1870 X + 7.7571 Y + -20.5105 Z - -1.7175 = 0 0.0116 0.0042 0.0254 0.0206 Atom X Y Z Distance Esd C2 7.5768 9.1880 17.8120 - 0.0219 ± 0.0016 C5 8.8217 7.4913 15.8714 0.0198 ± 0.0013 C10 7.4533 7.7414 15.8607 - 0.0413 ± 0.0013 N1 6.9094 8.6685 16.7826 0.0433 ± 0.0011 Chi Squared = 2992.3 Orthonormal Equation of Plane 3 0.1422 X + 0.7574 Y + -0.6373 Z - -3.1903 = 0 0.0006 0.0004 0.0004 0.0101 Crystallographic Equation of Plane 1.6105 X + 7.4640 Y + -22.3137 Z - -3.1903 = 0 0.0065 0.0036 0.0149 0.0101 Atom X Y Z Distance Esd C5 8.8217 7.4913 15.8714 0.0034 ± 0.0013 C6 9.3359 6.6001 14.9501 - 0.0112 ± 0.0014 C7 8.5265 5.9861 14.0055 0.0106 ± 0.0013 C8 7.1667 6.2280 14.0097 - 0.0022 ± 0.0014 C9 6.6414 7.1088 14.9444 - 0.0056 ± 0.0014 C10 7.4533 7.7414 15.8607 0.0050 ± 0.0013 Chi Squared = 170.4 Orthonormal Equation of Plane 4 0.7906 X + 0.0479 Y + -0.6104 Z - 0.7349 = 0 0.0006 0.0022 0.0007 0.0108 Crystallographic Equation of Plane 8.9531 X + 0.4719 Y + -21.3715 Z - 0.7349 = 0 0.0068 0.0218 0.0250 0.0108 Atom X Y Z Distance Esd C16 7.1994 2.4774 8.3155 0.0000 ± 0.0014 C15 7.8305 3.4754 9.2113 0.0000 ± 0.0016 C14 8.6833 2.8146 10.2641 0.0000 ± 0.0016 Orthonormal Equation of Plane 5 0.7893 X + 0.0428 Y + -0.6125 Z - 0.6872 = 0 0.0006 0.0024 0.0007 0.0126 Crystallographic Equation of Plane 8.9379 X + 0.4217 Y + -21.4453 Z - 0.6872 = 0 0.0066 0.0236 0.0245 0.0126 Atom X Y Z Distance Esd C15 7.8305 3.4754 9.2113 0.0000 ± 0.0016 C14 8.6833 2.8146 10.2641 0.0000 ± 0.0016 C13 9.3757 3.7680 11.2229 0.0000 ± 0.0016 Orthonormal Equation of Plane 6 -0.1314 X + 0.7488 Y + -0.6497 Z - -5.7018 = 0 0.0021 0.0007 0.0006 0.0222 Crystallographic Equation of Plane -1.4878 X + 7.3793 Y + -22.7464 Z - -5.7018 = 0 0.0243 0.0064 0.0215 0.0222 Atom X Y Z Distance Esd C14 8.6833 2.8146 10.2641 0.0000 ± 0.0015 C13 9.3757 3.7680 11.2229 0.0000 ± 0.0015 C12 8.4180 4.4256 12.1745 0.0000 ± 0.0014 Orthonormal Equation of Plane 7 -0.0612 X + 0.7912 Y + -0.6084 Z - -4.4211 = 0 0.0018 0.0004 0.0006 0.0182 Crystallographic Equation of Plane -0.6934 X + 7.7979 Y + -21.3022 Z - -4.4211 = 0 0.0209 0.0044 0.0205 0.0182 Atom X Y Z Distance Esd C13 9.3757 3.7680 11.2229 0.0000 ± 0.0015 C12 8.4180 4.4256 12.1745 0.0000 ± 0.0013 O11 9.1882 5.1952 13.0978 0.0000 ± 0.0009 Orthonormal Equation of Plane 8 0.0184 X + 0.7604 Y + -0.6492 Z - -4.3831 = 0 0.0019 0.0005 0.0006 0.0189 Crystallographic Equation of Plane 0.2082 X + 7.4942 Y + -22.7285 Z - -4.3831 = 0 0.0212 0.0050 0.0208 0.0189 Atom X Y Z Distance Esd C12 8.4180 4.4256 12.1745 0.0000 ± 0.0013 O11 9.1882 5.1952 13.0978 0.0000 ± 0.0010 C7 8.5265 5.9861 14.0055 0.0000 ± 0.0013 Dihedral Angles Between Planes: ——————————- Plane No. Plane No. Dihedral Angle ——— ——— ————– 1 2 59.85 ± 0.07 1 3 57.74 ± 0.05 1 4 113.40 ± 0.10 1 5 113.51 ± 0.10 1 6 42.95 ± 0.15 1 7 45.80 ± 0.12 1 8 50.99 ± 0.11 2 3 4.49 ± 0.51 2 4 56.77 ± 0.14 2 5 56.98 ± 0.15 2 6 19.17 ± 0.17 2 7 14.67 ± 0.19 2 8 10.77 ± 0.26 3 4 57.47 ± 0.12 3 5 57.65 ± 0.13 3 6 15.75 ± 0.17 3 7 11.95 ± 0.19 3 8 7.13 ± 0.33 4 5 0.33 ± 4.31 4 6 70.82 ± 0.15 4 7 68.85 ± 0.14 4 8 63.44 ± 0.15 5 6 70.96 ± 0.15 5 7 69.01 ± 0.15 5 8 63.60 ± 0.15 6 7 5.26 ± 0.54 6 8 8.62 ± 0.33 7 8 5.42 ± 0.46 |
Refinement. Refinement of F against all reflections. The weighted R-factor wR and goodness of fit S are based on F, conventional R-factors R are based on F, with F set to zero or negative F2. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O2 | 0.62329 (9) | 1.0167 (1) | 0.53035 (4) | 0.0916 (7) | |
O11 | 0.81141 (7) | 0.52716 (9) | 0.37410 (3) | 0.0619 (6) | |
N1 | 0.6102 (1) | 0.8796 (1) | 0.47935 (4) | 0.0577 (7) | |
N17 | 0.5564 (1) | 0.1602 (1) | 0.24818 (4) | 0.0714 (8) | |
N18 | 0.5322 (1) | 0.0844 (1) | 0.21678 (4) | 0.0715 (8) | |
N19 | 0.5934 (1) | 0.1252 (1) | 0.18792 (4) | 0.0647 (7) | |
N20 | 0.65938 (9) | 0.23081 (9) | 0.20057 (3) | 0.0493 (6) | |
C2 | 0.6691 (1) | 0.9323 (2) | 0.50875 (5) | 0.0689 (9) | |
C3 | 0.7882 (2) | 0.8711 (2) | 0.51669 (6) | 0.065 (1) | 0.800 |
C4 | 0.8548 (2) | 0.8434 (2) | 0.47936 (6) | 0.057 (1) | 0.800 |
C5 | 0.7790 (1) | 0.7601 (1) | 0.45332 (4) | 0.0506 (8) | |
C6 | 0.8245 (1) | 0.6697 (1) | 0.42701 (4) | 0.0532 (8) | |
C7 | 0.7530 (1) | 0.6074 (1) | 0.40002 (4) | 0.0503 (8) | |
C8 | 0.6329 (1) | 0.6319 (1) | 0.40015 (4) | 0.0557 (8) | |
C9 | 0.5865 (1) | 0.7213 (1) | 0.42684 (5) | 0.0563 (8) | |
C10 | 0.6582 (1) | 0.7855 (1) | 0.45302 (4) | 0.0497 (8) | |
C12 | 0.7434 (1) | 0.4491 (1) | 0.34773 (4) | 0.0543 (8) | |
C13 | 0.8280 (1) | 0.3823 (1) | 0.32055 (5) | 0.0625 (9) | |
C14 | 0.7668 (1) | 0.2856 (1) | 0.29316 (5) | 0.0655 (9) | |
C15 | 0.6915 (1) | 0.3526 (1) | 0.26309 (5) | 0.0605 (9) | |
C16 | 0.6358 (1) | 0.2514 (1) | 0.23751 (4) | 0.0525 (8) | |
C21 | 0.7463 (1) | 0.2946 (1) | 0.17484 (4) | 0.0493 (8) | |
C22 | 0.8558 (1) | 0.2070 (1) | 0.17191 (5) | 0.0567 (8) | |
C23 | 0.9458 (1) | 0.2710 (1) | 0.14548 (5) | 0.065 (1) | |
C24 | 0.8936 (1) | 0.3009 (1) | 0.10667 (5) | 0.072 (1) | |
C25 | 0.7839 (1) | 0.3889 (1) | 0.11007 (5) | 0.069 (1) | |
C26 | 0.6929 (1) | 0.3238 (1) | 0.13606 (5) | 0.0593 (9) | |
C3A | 0.8115 | 0.9432 | 0.5000 | 0.0577 | 0.200 |
C4A | 0.8475 | 0.8030 | 0.4916 | 0.0449 | 0.200 |
H1 | 0.5305 | 0.9070 | 0.4758 | 0.0753* | |
H3a | 0.7775 | 0.7837 | 0.5308 | 0.0865* | 0.800 |
H3b | 0.8353 | 0.9353 | 0.5327 | 0.0865* | 0.800 |
H4a | 0.9294 | 0.7930 | 0.4851 | 0.0750* | 0.800 |
H4b | 0.8744 | 0.9315 | 0.4667 | 0.0750* | 0.800 |
H6 | 0.9108 | 0.6487 | 0.4274 | 0.0696* | |
H8 | 0.5801 | 0.5860 | 0.3813 | 0.0726* | |
H9 | 0.4996 | 0.7394 | 0.4271 | 0.0739* | |
H12a | 0.6882 | 0.5096 | 0.3334 | 0.0706* | |
H12b | 0.6970 | 0.3785 | 0.3617 | 0.0706* | |
H13a | 0.8877 | 0.3303 | 0.3357 | 0.0814* | |
H13b | 0.8687 | 0.4544 | 0.3054 | 0.0814* | |
H14a | 0.7151 | 0.2239 | 0.3085 | 0.0854* | |
H14b | 0.8290 | 0.2310 | 0.2799 | 0.0854* | |
H15a | 0.7422 | 0.4145 | 0.2475 | 0.0799* | |
H15b | 0.6282 | 0.4066 | 0.2760 | 0.0799* | |
H21 | 0.7702 | 0.3840 | 0.1859 | 0.0642* | |
H22a | 0.8332 | 0.1158 | 0.1617 | 0.0744* | |
H22b | 0.8913 | 0.1963 | 0.1979 | 0.0744* | |
H23a | 1.0138 | 0.2073 | 0.1423 | 0.0860* | |
H23b | 0.9742 | 0.3577 | 0.1571 | 0.0860* | |
H24a | 0.8720 | 0.2135 | 0.0940 | 0.0939* | |
H24b | 0.9537 | 0.3495 | 0.0908 | 0.0939* | |
H25a | 0.7487 | 0.4015 | 0.0841 | 0.0912* | |
H25b | 0.8067 | 0.4792 | 0.1208 | 0.0912* | |
H26a | 0.6244 | 0.3868 | 0.1392 | 0.0771* | |
H26b | 0.6652 | 0.2369 | 0.1244 | 0.0771* | |
H3Aa | 0.8547 | 0.9789 | 0.5228 | 0.0756* | 0.200 |
H3Ab | 0.8267 | 1.0035 | 0.4776 | 0.0756* | 0.200 |
H4Aa | 0.8248 | 0.7417 | 0.5132 | 0.0612* | 0.200 |
H4Ab | 0.9348 | 0.7983 | 0.4876 | 0.0612* | 0.200 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0778 (7) | 0.1194 (7) | 0.0828 (8) | 0.0330 (6) | −0.0203 (7) | −0.0503 (7) |
O11 | 0.0545 (5) | 0.0722 (5) | 0.0604 (7) | −0.0049 (5) | 0.0039 (6) | −0.0181 (5) |
N1 | 0.0517 (6) | 0.0644 (6) | 0.0577 (8) | 0.0068 (6) | −0.0049 (6) | −0.0103 (6) |
N17 | 0.0683 (8) | 0.0733 (7) | 0.073 (1) | −0.0095 (6) | 0.0178 (7) | −0.0015 (7) |
N18 | 0.0607 (7) | 0.0710 (7) | 0.085 (1) | −0.0152 (6) | 0.0123 (7) | −0.0077 (7) |
N19 | 0.0592 (7) | 0.0631 (6) | 0.073 (1) | −0.0180 (6) | 0.0046 (7) | −0.0137 (7) |
N20 | 0.0460 (6) | 0.0473 (5) | 0.0551 (8) | −0.0074 (5) | 0.0014 (6) | −0.0083 (6) |
C2 | 0.0646 (9) | 0.0846 (9) | 0.060 (1) | 0.0153 (8) | −0.0120 (9) | −0.0186 (9) |
C3 | 0.063 (1) | 0.084 (1) | 0.053 (1) | 0.015 (1) | −0.010 (1) | −0.016 (1) |
C4 | 0.055 (1) | 0.070 (1) | 0.049 (1) | −0.0014 (9) | −0.003 (1) | −0.002 (1) |
C5 | 0.0475 (8) | 0.0570 (7) | 0.0479 (9) | −0.0016 (6) | −0.0027 (7) | −0.0013 (7) |
C6 | 0.0465 (8) | 0.0612 (7) | 0.053 (1) | −0.0012 (7) | −0.0005 (7) | −0.0015 (8) |
C7 | 0.0524 (8) | 0.0509 (6) | 0.0478 (9) | −0.0037 (7) | 0.0034 (7) | −0.0004 (7) |
C8 | 0.0527 (8) | 0.0609 (7) | 0.054 (1) | −0.0059 (7) | −0.0036 (8) | −0.0052 (8) |
C9 | 0.0467 (7) | 0.0665 (8) | 0.057 (1) | −0.0007 (7) | −0.0038 (7) | −0.0043 (8) |
C10 | 0.0521 (7) | 0.0499 (7) | 0.0471 (9) | 0.0015 (6) | −0.0004 (7) | −0.0000 (7) |
C12 | 0.0570 (8) | 0.0522 (7) | 0.054 (1) | −0.0066 (7) | −0.0021 (8) | −0.0060 (7) |
C13 | 0.0605 (9) | 0.0662 (8) | 0.061 (1) | 0.0043 (7) | −0.0013 (8) | −0.0092 (8) |
C14 | 0.0700 (9) | 0.0594 (8) | 0.068 (1) | 0.0130 (7) | −0.0044 (9) | −0.0144 (8) |
C15 | 0.077 (1) | 0.0557 (7) | 0.052 (1) | 0.0025 (7) | 0.0012 (9) | −0.0059 (8) |
C16 | 0.0530 (8) | 0.0512 (6) | 0.053 (1) | 0.0029 (6) | 0.0045 (8) | −0.0032 (7) |
C21 | 0.0491 (7) | 0.0470 (7) | 0.0521 (9) | −0.0074 (6) | 0.0015 (7) | −0.0056 (7) |
C22 | 0.0474 (7) | 0.0674 (8) | 0.057 (1) | 0.0006 (7) | −0.0066 (8) | 0.0018 (8) |
C23 | 0.0514 (8) | 0.0773 (9) | 0.070 (1) | −0.0020 (8) | 0.0075 (8) | −0.0056 (9) |
C24 | 0.077 (1) | 0.0784 (9) | 0.061 (1) | −0.0002 (9) | 0.0131 (9) | −0.0018 (9) |
C25 | 0.083 (1) | 0.0681 (8) | 0.059 (1) | 0.0008 (8) | 0.0018 (9) | 0.0064 (9) |
C26 | 0.0595 (8) | 0.0566 (7) | 0.062 (1) | 0.0058 (7) | −0.0051 (8) | 0.0015 (8) |
C3A | 0.0543 | 0.068 (4) | 0.052 (5) | 0.004 (3) | −0.008 (4) | 0.008 (4) |
C4A | 0.0480 | 0.063 (4) | 0.030 (4) | −0.013 (3) | −0.007 (3) | 0.016 (3) |
O2—C2 | 1.238 (2) | C12—H12b | 1.000 |
O11—C7 | 1.374 (2) | C13—C14 | 1.519 (2) |
O11—C12 | 1.428 (2) | C13—H13a | 1.000 |
N1—C2 | 1.332 (2) | C13—H13b | 1.000 |
N1—C10 | 1.416 (2) | C14—C15 | 1.507 (2) |
N1—H1 | 0.950 | C14—H14a | 1.000 |
N17—N18 | 1.357 (2) | C14—H14b | 1.000 |
N17—C16 | 1.325 (2) | C15—C16 | 1.482 (2) |
N18—N19 | 1.290 (2) | C15—H15a | 1.000 |
N19—N20 | 1.355 (2) | C15—H15b | 1.000 |
N20—C16 | 1.336 (2) | C21—C22 | 1.514 (2) |
N20—C21 | 1.475 (2) | C21—C26 | 1.514 (2) |
C2—C3 | 1.503 (3) | C21—H21 | 1.000 |
C2—C3A | 1.645 | C22—C23 | 1.514 (2) |
C3—C4 | 1.533 (4) | C22—H22a | 1.000 |
C3—H3a | 1.000 | C22—H22b | 1.000 |
C3—H3b | 1.000 | C23—C24 | 1.511 (3) |
C4—C5 | 1.497 (3) | C23—H23a | 1.000 |
C4—H4a | 1.000 | C23—H23b | 1.000 |
C4—H4b | 1.000 | C24—C25 | 1.519 (2) |
C5—C6 | 1.381 (2) | C24—H24a | 1.000 |
C5—C10 | 1.391 (2) | C24—H24b | 1.000 |
C5—C4A | 1.606 | C25—C26 | 1.517 (2) |
C6—C7 | 1.387 (2) | C25—H25a | 1.000 |
C6—H6 | 1.000 | C25—H25b | 1.000 |
C7—C8 | 1.381 (2) | C26—H26a | 1.000 |
C8—C9 | 1.388 (2) | C26—H26b | 1.000 |
C8—H8 | 1.000 | C3A—C4A | 1.4702 |
C9—C10 | 1.378 (2) | C3A—H3Aa | 1.0000 |
C9—H9 | 1.000 | C3A—H3Ab | 1.0000 |
C12—C13 | 1.502 (2) | C4A—H4Aa | 1.0000 |
C12—H12a | 1.000 | C4A—H4Ab | 1.0000 |
C7—O11—C12 | 118.5 (1) | C15—C14—H14b | 108.1 |
C2—N1—C10 | 124.5 (1) | H14a—C14—H14b | 109.5 |
C2—N1—H1 | 117.8 | C14—C15—C16 | 111.6 (1) |
C10—N1—H1 | 117.8 | C14—C15—H15a | 108.9 |
N18—N17—C16 | 106.4 (1) | C14—C15—H15b | 108.9 |
N17—N18—N19 | 110.7 (1) | C16—C15—H15a | 108.9 |
N18—N19—N20 | 106.3 (1) | C16—C15—H15b | 108.9 |
N19—N20—C16 | 108.8 (1) | H15a—C15—H15b | 109.5 |
N19—N20—C21 | 119.7 (1) | N17—C16—N20 | 107.8 (1) |
C16—N20—C21 | 131.3 (1) | N17—C16—C15 | 125.1 (2) |
N1—C2—C3 | 115.8 (2) | N20—C16—C15 | 127.0 (1) |
N1—C2—C3A | 111.9 | N20—C21—C22 | 110.2 (1) |
C2—C3—C4 | 110.8 (2) | N20—C21—C26 | 111.3 (1) |
C2—C3—H3a | 109.1 | N20—C21—H21 | 108.7 |
C2—C3—H3b | 109.1 | C22—C21—C26 | 112.0 (1) |
C4—C3—H3a | 109.1 | C22—C21—H21 | 107.9 |
C4—C3—H3b | 109.1 | C26—C21—H21 | 106.7 |
H3a—C3—H3b | 109.5 | C21—C22—C23 | 110.8 (1) |
C3—C4—C5 | 109.5 (2) | C21—C22—H22a | 109.1 |
C3—C4—H4a | 109.5 | C21—C22—H22b | 109.1 |
C3—C4—H4b | 109.5 | C23—C22—H22a | 109.1 |
C5—C4—H4a | 109.5 | C23—C22—H22b | 109.1 |
C5—C4—H4b | 109.5 | H22a—C22—H22b | 109.5 |
H4a—C4—H4b | 109.5 | C22—C23—C24 | 111.6 (1) |
C4—C5—C6 | 123.1 (2) | C22—C23—H23a | 108.9 |
C4—C5—C10 | 118.0 (2) | C22—C23—H23b | 108.9 |
C6—C5—C10 | 118.5 (1) | C24—C23—H23a | 108.9 |
C6—C5—C4A | 123.2 | C24—C23—H23b | 108.9 |
C10—C5—C4A | 115.7 | H23a—C23—H23b | 109.5 |
C5—C6—C7 | 121.5 (1) | C23—C24—C25 | 111.1 (2) |
C5—C6—H6 | 119.2 | C23—C24—H24a | 109.1 |
C7—C6—H6 | 119.2 | C23—C24—H24b | 109.0 |
O11—C7—C6 | 115.1 (1) | C25—C24—H24a | 109.1 |
O11—C7—C8 | 125.2 (1) | C25—C24—H24b | 109.1 |
C6—C7—C8 | 119.7 (1) | H24a—C24—H24b | 109.5 |
C7—C8—C9 | 119.1 (1) | C24—C25—C26 | 111.2 (1) |
C7—C8—H8 | 120.5 | C24—C25—H25a | 109.1 |
C9—C8—H8 | 120.5 | C24—C25—H25b | 109.1 |
C8—C9—C10 | 121.1 (1) | C26—C25—H25a | 109.0 |
C8—C9—H9 | 119.5 | C26—C25—H25b | 109.0 |
C10—C9—H9 | 119.5 | H25a—C25—H25b | 109.5 |
N1—C10—C5 | 119.4 (1) | C21—C26—C25 | 110.3 (1) |
N1—C10—C9 | 120.5 (1) | C21—C26—H26a | 109.3 |
C5—C10—C9 | 120.1 (1) | C21—C26—H26b | 109.3 |
O11—C12—C13 | 107.6 (1) | C25—C26—H26a | 109.3 |
O11—C12—H12a | 109.9 | C25—C26—H26b | 109.3 |
O11—C12—H12b | 109.9 | H26a—C26—H26b | 109.5 |
C13—C12—H12a | 109.9 | C2—C3A—C4A | 104.33 |
C13—C12—H12b | 109.9 | C2—C3A—H3Aa | 110.74 |
H12a—C12—H12b | 109.5 | C2—C3A—H3Ab | 110.74 |
C12—C13—C14 | 112.6 (1) | C4A—C3A—H3Aa | 110.74 |
C12—C13—H13a | 108.7 | C4A—C3A—H3Ab | 110.74 |
C12—C13—H13b | 108.7 | H3Aa—C3A—H3Ab | 109.47 |
C14—C13—H13a | 108.7 | C5—C4A—C3A | 106.25 |
C14—C13—H13b | 108.7 | C5—C4A—H4Aa | 110.27 |
H13a—C13—H13b | 109.5 | C5—C4A—H4Ab | 110.27 |
C13—C14—C15 | 115.1 (1) | C3A—C4A—H4Aa | 110.27 |
C13—C14—H14a | 108.1 | C3A—C4A—H4Ab | 110.27 |
C13—C14—H14b | 108.1 | H4Aa—C4A—H4Ab | 109.47 |
C15—C14—H14a | 108.1 | ||
C12—O11—C7—C6 | 174.0 (1) | C4A—C5—C6—C7 | 162.6 |
C12—O11—C7—C8 | −8.0 (2) | C4—C5—C10—N1 | −5.4 (2) |
C7—O11—C12—C13 | 174.6 (1) | C4—C5—C10—C9 | 173.4 (1) |
C10—N1—C2—O2 | 178.3 (1) | C6—C5—C10—N1 | −179.0 (1) |
C10—N1—C2—C3 | −8.7 (2) | C6—C5—C10—C9 | −0.1 (2) |
C10—N1—C2—C3A | 29.5 (2) | C4A—C5—C10—N1 | 18.7 |
C2—N1—C10—C5 | −10.6 (2) | C4A—C5—C10—C9 | −162.4 |
C2—N1—C10—C9 | 170.5 (1) | C6—C5—C4A—C3A | 149.1 |
C16—N17—N18—N19 | 0.3 (2) | C10—C5—C4A—C3A | −49.5 |
N18—N17—C16—N20 | −0.3 (1) | C5—C6—C7—O11 | 175.8 (1) |
N18—N17—C16—C15 | −177.5 (1) | C5—C6—C7—C8 | −2.4 (2) |
N17—N18—N19—N20 | −0.2 (1) | O11—C7—C8—C9 | −176.5 (1) |
N18—N19—N20—C21 | 175.6 (1) | C6—C7—C8—C9 | 1.5 (2) |
N19—N20—C16—N17 | 0.2 (2) | C7—C8—C9—C10 | 0.1 (2) |
N19—N20—C16—C15 | 177.3 (1) | C8—C9—C10—N1 | 178.1 (1) |
C21—N20—C16—N17 | −174.8 (1) | C8—C9—C10—C5 | −0.8 (2) |
C21—N20—C16—C15 | 2.4 (2) | O11—C12—C13—C14 | 174.7 (1) |
N19—N20—C21—C22 | −77.3 (1) | C12—C13—C14—C15 | 71.0 (2) |
N19—N20—C21—C26 | 47.5 (1) | C13—C14—C15—C16 | 179.7 (1) |
C16—N20—C21—C22 | 97.2 (1) | C14—C15—C16—N17 | 64.9 (2) |
C16—N20—C21—C26 | −138.0 (1) | C14—C15—C16—N20 | −111.7 (2) |
O2—C2—C3—C4 | −146.2 (2) | N20—C21—C22—C23 | 179.9 (1) |
N1—C2—C3—C4 | 40.9 (2) | C26—C21—C22—C23 | 55.5 (1) |
O2—C2—C3A—C4A | 152.0 | N20—C21—C26—C25 | −179.8 (1) |
N1—C2—C3A—C4A | −58.2 | C22—C21—C26—C25 | −56.1 (1) |
C2—C3—C4—C5 | −53.4 (2) | C21—C22—C23—C24 | −54.8 (2) |
C3—C4—C5—C6 | −150.0 (1) | C22—C23—C24—C25 | 55.4 (2) |
C3—C4—C5—C10 | 36.8 (2) | C23—C24—C25—C26 | −56.0 (2) |
C4—C5—C6—C7 | −171.5 (1) | C24—C25—C26—C21 | 55.9 (2) |
C10—C5—C6—C7 | 1.7 (2) | C2—C3A—C4A—C5 | 64.24 |
C20H27N5O2 | F(000) = 792 |
Mr = 369.47 | Dx = 1.26 Mg m−3 |
Monoclinic, P21/n | Melting point: 419 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.148 (1) Å | Cell parameters from 3878 reflections |
b = 10.739 (1) Å | θ = 1.4–27.5° |
c = 35.279 (1) Å | µ = 0.08 mm−1 |
β = 94.070 (1)° | T = 294 K |
V = 1945.3 (6) Å3 | Plate, colourless |
Z = 4 | 0.22 × 0.12 × 0.06 mm |
95mm CCD camera on κ-goniometer diffractometer | 2223 reflections with I > 2σ(I) |
Radiation source: fine-focued sealed tube | Rint = 0.026 |
Horizontally mounted graphite crystal monochromator | θmax = 27.5°, θmin = 2.5° |
Detector resolution: 9 pixels mm-1 | h = 0→6 |
CCD scans | k = 0→13 |
4572 measured reflections | l = −45→45 |
4343 independent reflections |
Refinement on F | 0 constraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.043 | w = 4Fo2/[σ2(Fo2) + 0.0004Fo4] |
wR(F2) = 0.041 | (Δ/σ)max = 0.001 |
S = 4.19 | Δρmax = 0.13 e Å−3 |
2223 reflections | Δρmin = −0.12 e Å−3 |
245 parameters | Extinction correction: isotropic (Zachariasen, 1963), eq. 22, p. 292 in Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291-294. Copenhagen: Munksgaard. |
108 restraints | Extinction coefficient: 3.7536 × 10-06 |
C20H27N5O2 | V = 1945.3 (6) Å3 |
Mr = 369.47 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.148 (1) Å | µ = 0.08 mm−1 |
b = 10.739 (1) Å | T = 294 K |
c = 35.279 (1) Å | 0.22 × 0.12 × 0.06 mm |
β = 94.070 (1)° |
95mm CCD camera on κ-goniometer diffractometer | 2223 reflections with I > 2σ(I) |
4572 measured reflections | Rint = 0.026 |
4343 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 108 restraints |
wR(F2) = 0.041 | H-atom parameters constrained |
S = 4.19 | Δρmax = 0.13 e Å−3 |
2223 reflections | Δρmin = −0.12 e Å−3 |
245 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedran 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 distance, 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) treatmemt of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Orthonormal Equation of Plane 1 0.6844 X + -0.6239 Y + -0.3772 Z - -15.0972 = 0 0.0006 0.0006 0.0007 0.0181 Crystallographic Equation of Plane 3.5231 X + -6.7005 Y + -14.9871 Z - -15.0972 = 0 0.0031 0.0067 0.0666 0.0181 Atom X Y Z Distance Esd C16 - 2.6850 5.3759 26.2505 0.0039 ± 0.0016 N17 - 1.9986 6.4168 25.7961 - 0.0044 ± 0.0014 N18 - 1.1299 6.7605 26.7833 0.0034 ± 0.0015 N19 - 1.2749 5.9843 27.8154 - 0.0010 ± 0.0014 N20 - 2.2604 5.1020 27.4892 - 0.0018 ± 0.0013 Chi Squared = 23.4 Orthonormal Equation of Plane 2 -0.7705 X + -0.0216 Y + -0.6371 Z - -13.6084 = 0 0.0006 0.0012 0.0007 0.0109 Crystallographic Equation of Plane -3.9662 X + -0.2318 Y + -20.4892 Z - -13.6084 = 0 0.0030 0.0128 0.0661 0.0109 Atom X Y Z Distance Esd C2 3.3818 1.9396 17.1523 0.0335 ± 0.0017 C5 1.8065 3.3243 19.1112 - 0.0307 ± 0.0015 C10 1.8062 1.9366 19.0104 0.0638 ± 0.0015 N1 2.7206 1.3025 18.1306 - 0.0666 ± 0.0013 Chi Squared = 4990.1 Orthonormal Equation of Plane 3 -0.7035 X + 0.0625 Y + -0.7079 Z - -14.5985 = 0 0.0005 0.0007 0.0005 0.0089 Crystallographic Equation of Plane -3.6213 X + 0.6711 Y + -23.1505 Z - -14.5985 = 0 0.0024 0.0070 0.0558 0.0089 Atom X Y Z Distance Esd C5 1.8065 3.3243 19.1112 0.0057 ± 0.0015 C6 0.9519 3.9202 20.0156 0.0039 ± 0.0015 C7 0.1041 3.1580 20.8102 - 0.0098 ± 0.0015 C8 0.0900 1.7852 20.6804 0.0061 ± 0.0016 C9 0.9507 1.1810 19.7755 0.0036 ± 0.0016 C10 1.8062 1.9366 19.0104 - 0.0095 ± 0.0015 Chi Squared = 119.0 Orthonormal Equation of Plane 4 0.0343 X + 0.6813 Y + -0.7312 Z - -15.6251 = 0 0.0024 0.0007 0.0006 0.0225 Crystallographic Equation of Plane 0.1765 X + 7.3161 Y + -25.8179 Z - -15.6251 = 0 0.0123 0.0077 0.1243 0.0225 Atom X Y Z Distance Esd C16 - 2.6850 5.3759 26.2505 0.0000 ± 0.0016 C15 - 3.6839 4.5971 25.4781 0.0000 ± 0.0017 C14 - 3.0329 3.5671 24.5489 0.0000 ± 0.0016 Orthonormal Equation of Plane 5 -0.8023 X + 0.0306 Y + -0.5961 Z - -12.0916 = 0 0.0006 0.0023 0.0008 0.0199 Crystallographic Equation of Plane -4.1300 X + 0.3285 Y + -18.9680 Z - -12.0916 = 0 0.0031 0.0247 0.0672 0.0199 Atom X Y Z Distance Esd C15 - 3.6839 4.5971 25.4781 0.0000 ± 0.0016 C14 - 3.0329 3.5671 24.5489 0.0000 ± 0.0016 C13 - 2.1950 4.1826 23.4528 0.0000 ± 0.0016 Orthonormal Equation of Plane 6 -0.7965 X + 0.0075 Y + -0.6046 Z - -12.4010 = 0 0.0006 0.0024 0.0008 0.0185 Crystallographic Equation of Plane -4.0999 X + 0.0801 Y + -19.2824 Z - -12.4010 = 0 0.0030 0.0255 0.0661 0.0185 Atom X Y Z Distance Esd C14 - 3.0329 3.5671 24.5489 0.0000 ± 0.0016 C13 - 2.1950 4.1826 23.4528 0.0000 ± 0.0016 C12 - 1.5358 3.1617 22.5719 0.0000 ± 0.0016 Orthonormal Equation of Plane 7 -0.7542 X + 0.0758 Y + -0.6522 Z - -13.3241 = 0 0.0006 0.0022 0.0006 0.0169 Crystallographic Equation of Plane -3.8824 X + 0.8142 Y + -21.0632 Z - -13.3241 = 0 0.0029 0.0232 0.0633 0.0169 Atom X Y Z Distance Esd C13 - 2.1950 4.1826 23.4528 0.0000 ± 0.0016 C12 - 1.5358 3.1617 22.5719 0.0000 ± 0.0016 O11 - 0.6876 3.8790 21.6744 0.0000 ± 0.0011 Orthonormal Equation of Plane 8 -0.7319 X + 0.0130 Y + -0.6813 Z - -14.2132 = 0 0.0006 0.0021 0.0007 0.0170 Crystallographic Equation of Plane -3.7674 X + 0.1399 Y + -22.1422 Z - -14.2132 = 0 0.0033 0.0231 0.0674 0.0170 Atom X Y Z Distance Esd C12 - 1.5358 3.1617 22.5719 0.0000 ± 0.0016 O11 - 0.6876 3.8790 21.6744 0.0000 ± 0.0011 C7 0.1041 3.1580 20.8102 0.0000 ± 0.0015 Dihedral Angles Between Planes: ——————————- Plane No. Plane No. Dihedral Angle ——— ——— ————– 1 2 105.88 ± 0.07 1 3 104.68 ± 0.05 1 4 97.23 ± 0.11 1 5 110.08 ± 0.10 1 6 108.77 ± 0.10 1 7 108.51 ± 0.09 1 8 104.60 ± 0.09 2 3 7.38 ± 0.36 2 4 64.87 ± 0.13 2 5 4.22 ± 0.73 2 6 2.91 ± 1.03 2 7 5.73 ± 0.51 2 8 3.91 ± 0.78 3 4 57.58 ± 0.12 3 5 8.75 ± 0.32 3 6 8.57 ± 0.32 3 7 4.38 ± 0.57 3 8 3.61 ± 0.73 4 5 64.58 ± 0.16 4 6 65.17 ± 0.16 4 7 59.82 ± 0.16 4 8 61.19 ± 0.16 5 6 1.45 ± 2.02 5 7 4.97 ± 0.60 5 8 6.42 ± 0.48 6 7 5.35 ± 0.55 6 8 5.76 ± 0.53 7 8 4.17 ± 0.70 |
Refinement. Refinement of F against all reflections. The weighted R-factor wR and goodness of fit S are based on F, conventional R-factors R are based on F, with F set to zero or negative F2. |
x | y | z | Uiso*/Ueq | ||
O2 | 1.0499 (2) | 0.1281 (1) | 0.46767 (3) | 0.0866 (8) | |
O11 | 0.1660 (2) | 0.3612 (1) | 0.61593 (3) | 0.0645 (7) | |
N1 | 0.7791 (3) | 0.1215 (1) | 0.51521 (3) | 0.0578 (8) | |
N17 | −0.0317 (3) | 0.5975 (1) | 0.73305 (3) | 0.0632 (9) | |
N18 | 0.1507 (3) | 0.6295 (1) | 0.76112 (4) | 0.0665 (9) | |
N19 | 0.1369 (3) | 0.5572 (1) | 0.79044 (4) | 0.0629 (9) | |
N20 | −0.0590 (2) | 0.4751 (1) | 0.78118 (3) | 0.0503 (8) | |
C2 | 0.8942 (3) | 0.1806 (2) | 0.48742 (4) | 0.061 (1) | |
C3 | 0.8149 (3) | 0.3143 (2) | 0.48132 (4) | 0.064 (1) | |
C4 | 0.7883 (3) | 0.3818 (2) | 0.51839 (4) | 0.054 (1) | |
C5 | 0.6152 (3) | 0.3095 (1) | 0.54308 (4) | 0.0443 (9) | |
C6 | 0.4615 (3) | 0.3650 (1) | 0.56880 (4) | 0.048 (1) | |
C7 | 0.3078 (3) | 0.2941 (2) | 0.59138 (4) | 0.049 (1) | |
C8 | 0.3034 (3) | 0.1662 (2) | 0.58768 (4) | 0.055 (1) | |
C9 | 0.4580 (3) | 0.1099 (1) | 0.56197 (4) | 0.055 (1) | |
C10 | 0.6137 (3) | 0.1804 (2) | 0.54022 (4) | 0.048 (1) | |
C12 | 0.0137 (3) | 0.2944 (2) | 0.64144 (4) | 0.054 (1) | |
C13 | −0.1022 (3) | 0.3894 (2) | 0.66646 (4) | 0.058 (1) | |
C14 | −0.2498 (3) | 0.3322 (2) | 0.69761 (4) | 0.054 (1) | |
C15 | −0.3635 (3) | 0.4281 (2) | 0.72403 (4) | 0.054 (1) | |
C16 | −0.1587 (3) | 0.5006 (2) | 0.74598 (4) | 0.0487 (9) | |
C21 | −0.1289 (3) | 0.3820 (2) | 0.80926 (4) | 0.052 (1) | |
C22 | 0.0921 (3) | 0.2927 (2) | 0.81763 (5) | 0.069 (1) | |
C23 | 0.0298 (4) | 0.1996 (2) | 0.84818 (5) | 0.085 (1) | |
C24 | −0.0437 (4) | 0.2652 (2) | 0.88405 (5) | 0.082 (1) | |
C25 | −0.2698 (4) | 0.3524 (2) | 0.87509 (5) | 0.081 (1) | |
C26 | −0.2109 (3) | 0.4454 (2) | 0.84474 (5) | 0.069 (1) | |
H1 | 0.8104 | 0.0346 | 0.5183 | 0.0761* | |
H3a | 0.6438 | 0.3169 | 0.4660 | 0.0846* | |
H3b | 0.9499 | 0.3574 | 0.4671 | 0.0846* | |
H4a | 0.7106 | 0.4659 | 0.5130 | 0.0702* | |
H4b | 0.9643 | 0.3915 | 0.5320 | 0.0702* | |
H6 | 0.4608 | 0.4578 | 0.5712 | 0.0626* | |
H8 | 0.1899 | 0.1146 | 0.6034 | 0.0707* | |
H9 | 0.4562 | 0.0173 | 0.5592 | 0.0726* | |
H12a | 0.1264 | 0.2354 | 0.6571 | 0.0704* | |
H12b | −0.1276 | 0.2469 | 0.6269 | 0.0704* | |
H13a | −0.2246 | 0.4431 | 0.6504 | 0.0753* | |
H13b | 0.0417 | 0.4419 | 0.6784 | 0.0753* | |
H14a | −0.1283 | 0.2767 | 0.7132 | 0.0710* | |
H14b | −0.3963 | 0.2814 | 0.6856 | 0.0710* | |
H15a | −0.4708 | 0.3834 | 0.7423 | 0.0704* | |
H15b | −0.4766 | 0.4870 | 0.7083 | 0.0704* | |
H21 | −0.2812 | 0.3325 | 0.7985 | 0.0678* | |
H22a | 0.2514 | 0.3408 | 0.8265 | 0.0906* | |
H22b | 0.1256 | 0.2465 | 0.7938 | 0.0906* | |
H23a | 0.1864 | 0.1463 | 0.8544 | 0.1133* | |
H23b | −0.1190 | 0.1461 | 0.8383 | 0.1133* | |
H24a | 0.1091 | 0.3140 | 0.8950 | 0.1118* | |
H24b | −0.0941 | 0.2017 | 0.9029 | 0.1118* | |
H25a | −0.3077 | 0.3985 | 0.8987 | 0.1119* | |
H25b | −0.4260 | 0.3024 | 0.8660 | 0.1119* | |
H26a | −0.3706 | 0.4961 | 0.8381 | 0.0899* | |
H26b | −0.0670 | 0.5013 | 0.8549 | 0.0899* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.124 (1) | 0.0741 (9) | 0.0710 (7) | 0.0248 (8) | 0.0518 (6) | 0.0070 (7) |
O11 | 0.0722 (7) | 0.0555 (7) | 0.0670 (7) | 0.0043 (6) | 0.0314 (6) | −0.0014 (6) |
N1 | 0.083 (1) | 0.0457 (8) | 0.0510 (8) | 0.0106 (8) | 0.0246 (7) | 0.0019 (7) |
N17 | 0.072 (1) | 0.0615 (9) | 0.0570 (8) | −0.0094 (9) | 0.0151 (7) | 0.0014 (8) |
N18 | 0.075 (1) | 0.061 (1) | 0.0647 (9) | −0.0139 (8) | 0.0177 (7) | −0.0018 (8) |
N19 | 0.0670 (9) | 0.0612 (9) | 0.0606 (9) | −0.0167 (8) | 0.0102 (7) | −0.0062 (8) |
N20 | 0.0561 (8) | 0.0498 (8) | 0.0456 (7) | −0.0087 (7) | 0.0100 (6) | −0.0029 (7) |
C2 | 0.082 (1) | 0.060 (1) | 0.0461 (9) | 0.010 (1) | 0.0158 (9) | 0.0015 (9) |
C3 | 0.086 (1) | 0.060 (1) | 0.051 (1) | 0.005 (1) | 0.0185 (9) | 0.0065 (9) |
C4 | 0.055 (1) | 0.055 (1) | 0.053 (1) | 0.0011 (9) | 0.0098 (8) | 0.0040 (9) |
C5 | 0.0445 (9) | 0.046 (1) | 0.0422 (9) | 0.0026 (9) | 0.0030 (8) | 0.0002 (8) |
C6 | 0.052 (1) | 0.042 (1) | 0.0502 (9) | 0.0023 (9) | 0.0058 (8) | 0.0001 (8) |
C7 | 0.049 (1) | 0.052 (1) | 0.0461 (9) | 0.0068 (9) | 0.0083 (8) | −0.0031 (8) |
C8 | 0.058 (1) | 0.050 (1) | 0.056 (1) | −0.0005 (9) | 0.0148 (8) | 0.0026 (9) |
C9 | 0.071 (1) | 0.043 (1) | 0.055 (1) | 0.000 (1) | 0.0158 (9) | −0.0017 (9) |
C10 | 0.053 (1) | 0.050 (1) | 0.0421 (9) | 0.0075 (9) | 0.0065 (8) | −0.0005 (8) |
C12 | 0.055 (1) | 0.060 (1) | 0.0488 (9) | 0.000 (1) | 0.0119 (8) | 0.0016 (9) |
C13 | 0.064 (1) | 0.060 (1) | 0.0511 (9) | 0.001 (1) | 0.0163 (9) | −0.0031 (9) |
C14 | 0.055 (1) | 0.064 (1) | 0.0462 (9) | −0.007 (1) | 0.0073 (8) | −0.0019 (9) |
C15 | 0.054 (1) | 0.066 (1) | 0.0442 (9) | −0.002 (1) | 0.0102 (8) | 0.0016 (9) |
C16 | 0.054 (1) | 0.051 (1) | 0.0418 (8) | 0.0027 (9) | 0.0142 (7) | −0.0017 (8) |
C21 | 0.059 (1) | 0.056 (1) | 0.0420 (9) | −0.0143 (9) | 0.0067 (8) | −0.0014 (9) |
C22 | 0.084 (1) | 0.061 (1) | 0.065 (1) | 0.011 (1) | 0.014 (1) | 0.004 (1) |
C23 | 0.111 (2) | 0.072 (1) | 0.078 (1) | 0.002 (1) | 0.004 (1) | 0.017 (1) |
C24 | 0.088 (1) | 0.112 (2) | 0.057 (1) | −0.024 (1) | −0.006 (1) | 0.023 (1) |
C25 | 0.081 (1) | 0.127 (2) | 0.051 (1) | −0.007 (1) | 0.013 (1) | 0.014 (1) |
C26 | 0.073 (1) | 0.084 (1) | 0.053 (1) | 0.008 (1) | 0.0205 (9) | −0.001 (1) |
O2—C2 | 1.234 (2) | C12—H12a | 1.000 |
O11—C7 | 1.375 (2) | C12—H12b | 1.000 |
O11—C12 | 1.428 (2) | C13—C14 | 1.510 (2) |
N1—C2 | 1.341 (2) | C13—H13a | 1.000 |
N1—C10 | 1.418 (2) | C13—H13b | 1.000 |
N1—H1 | 0.952 | C14—C15 | 1.533 (2) |
N17—N18 | 1.360 (2) | C14—H14a | 1.000 |
N17—C16 | 1.326 (2) | C14—H14b | 1.000 |
N18—N19 | 1.300 (2) | C15—C16 | 1.484 (2) |
N19—N20 | 1.362 (2) | C15—H15a | 1.000 |
N20—C16 | 1.338 (2) | C15—H15b | 1.000 |
N20—C21 | 1.470 (2) | C21—C22 | 1.502 (5) |
C2—C3 | 1.504 (3) | C21—C26 | 1.511 (2) |
C3—C4 | 1.510 (2) | C21—H21 | 1.000 |
C3—H3a | 1.000 | C22—C23 | 1.521 (3) |
C3—H3b | 1.000 | C22—H22a | 1.000 |
C4—C5 | 1.505 (2) | C22—H22b | 1.000 |
C4—H4a | 1.000 | C23—C24 | 1.520 (3) |
C4—H4b | 1.000 | C23—H23a | 1.000 |
C5—C6 | 1.381 (2) | C23—H23b | 1.000 |
C5—C10 | 1.391 (2) | C24—C25 | 1.510 (3) |
C6—C7 | 1.389 (2) | C24—H24a | 1.000 |
C6—H6 | 1.000 | C24—H24b | 1.000 |
C7—C8 | 1.380 (3) | C25—C26 | 1.511 (3) |
C8—C9 | 1.387 (2) | C25—H25a | 1.000 |
C8—H8 | 1.000 | C25—H25b | 1.000 |
C9—C10 | 1.375 (2) | C26—H26a | 1.000 |
C9—H9 | 1.000 | C26—H26b | 1.000 |
C12—C13 | 1.500 (2) | ||
C7—O11—C12 | 118.3 (1) | H13a—C13—H13b | 109.4 |
C2—N1—C10 | 124.1 (2) | C13—C14—C15 | 113.7 (2) |
C2—N1—H1 | 118.0 | C13—C14—H14a | 108.4 |
C10—N1—H1 | 118.0 | C13—C14—H14b | 108.4 |
N18—N17—C16 | 106.2 (2) | C15—C14—H14a | 108.4 |
N17—N18—N19 | 110.8 (2) | C15—C14—H14b | 108.4 |
N18—N19—N20 | 106.1 (2) | H14a—C14—H14b | 109.4 |
N19—N20—C16 | 108.6 (2) | C14—C15—C16 | 112.5 (1) |
N19—N20—C21 | 119.4 (2) | C14—C15—H15a | 108.7 |
C16—N20—C21 | 132.0 (2) | C14—C15—H15b | 108.7 |
N1—C2—C3 | 115.3 (2) | C16—C15—H15a | 108.7 |
C2—C3—C4 | 112.0 (2) | C16—C15—H15b | 108.7 |
C2—C3—H3a | 108.8 | H15a—C15—H15b | 109.5 |
C2—C3—H3b | 108.8 | N17—C16—N20 | 108.3 (2) |
C4—C3—H3a | 108.8 | N17—C16—C15 | 125.6 (2) |
C4—C3—H3b | 108.8 | N20—C16—C15 | 126.0 (2) |
H3a—C3—H3b | 109.5 | N20—C21—C22 | 110.4 (1) |
C3—C4—C5 | 110.3 (2) | N20—C21—C26 | 110.4 (2) |
C3—C4—H4a | 109.3 | N20—C21—H21 | 109.2 |
C3—C4—H4b | 109.3 | C22—C21—C26 | 112.2 (2) |
C5—C4—H4a | 109.2 | C22—C21—H21 | 107.3 |
C5—C4—H4b | 109.3 | C26—C21—H21 | 107.3 |
H4a—C4—H4b | 109.5 | C21—C22—C23 | 111.4 (2) |
C4—C5—C6 | 123.2 (2) | C21—C22—H22a | 109.0 |
C4—C5—C10 | 118.2 (2) | C21—C22—H22b | 109.0 |
C6—C5—C10 | 118.5 (2) | C23—C22—H22a | 109.0 |
C5—C6—C7 | 121.1 (2) | C23—C22—H22b | 109.0 |
C5—C6—H6 | 119.5 | H22a—C22—H22b | 109.5 |
C7—C6—H6 | 119.5 | C22—C23—C24 | 111.3 (2) |
O11—C7—C6 | 115.0 (2) | C22—C23—H23a | 109.0 |
O11—C7—C8 | 125.1 (2) | C22—C23—H23b | 109.0 |
C6—C7—C8 | 119.9 (2) | C24—C23—H23a | 109.0 |
C7—C8—C9 | 119.3 (2) | C24—C23—H23b | 109.0 |
C7—C8—H8 | 120.3 | H23a—C23—H23b | 109.5 |
C9—C8—H8 | 120.4 | C23—C24—C25 | 110.3 (2) |
C8—C9—C10 | 120.7 (2) | C23—C24—H24a | 109.3 |
C8—C9—H9 | 119.7 | C23—C24—H24b | 109.3 |
C10—C9—H9 | 119.7 | C25—C24—H24a | 109.2 |
N1—C10—C5 | 119.3 (2) | C25—C24—H24b | 109.3 |
N1—C10—C9 | 120.1 (2) | H24a—C24—H24b | 109.5 |
C5—C10—C9 | 120.6 (2) | C24—C25—C26 | 111.6 (2) |
O11—C12—C13 | 106.8 (2) | C24—C25—H25a | 109.0 |
O11—C12—H12a | 110.2 | C24—C25—H25b | 108.9 |
O11—C12—H12b | 110.1 | C26—C25—H25a | 108.9 |
C13—C12—H12a | 110.1 | C26—C25—H25b | 108.9 |
C13—C12—H12b | 110.1 | H25a—C25—H25b | 109.5 |
H12a—C12—H12b | 109.4 | C21—C26—C25 | 111.8 (2) |
C12—C13—C14 | 113.1 (2) | C21—C26—H26a | 108.9 |
C12—C13—H13a | 108.6 | C21—C26—H26b | 108.9 |
C12—C13—H13b | 108.6 | C25—C26—H26a | 108.9 |
C14—C13—H13a | 108.6 | C25—C26—H26b | 108.9 |
C14—C13—H13b | 108.6 | H26a—C26—H26b | 109.5 |
C12—O11—C7—C6 | −176.9 (1) | C4—C5—C6—C7 | −179.0 (1) |
C12—O11—C7—C8 | 4.1 (2) | C10—C5—C6—C7 | −0.1 (2) |
C7—O11—C12—C13 | 175.8 (1) | C4—C5—C10—N1 | 1.8 (2) |
C10—N1—C2—O2 | 175.4 (1) | C4—C5—C10—C9 | −179.6 (1) |
C10—N1—C2—C3 | −6.2 (2) | C6—C5—C10—N1 | −177.2 (1) |
C2—N1—C10—C5 | −16.2 (2) | C6—C5—C10—C9 | 1.4 (2) |
C2—N1—C10—C9 | 165.2 (1) | C5—C6—C7—O11 | 179.6 (1) |
C16—N17—N18—N19 | −0.7 (2) | C5—C6—C7—C8 | −1.4 (2) |
N18—N17—C16—N20 | 0.8 (2) | O11—C7—C8—C9 | −179.5 (1) |
N18—N17—C16—C15 | −175.4 (1) | C6—C7—C8—C9 | 1.5 (2) |
N17—N18—N19—N20 | 0.4 (2) | C7—C8—C9—C10 | −0.2 (2) |
N18—N19—N20—C16 | 0.1 (2) | C8—C9—C10—N1 | 177.3 (1) |
N18—N19—N20—C21 | −178.2 (1) | C8—C9—C10—C5 | −1.3 (2) |
N19—N20—C16—N17 | −0.6 (2) | O11—C12—C13—C14 | −174.7 (1) |
N19—N20—C16—C15 | 175.6 (1) | C12—C13—C14—C15 | 178.5 (1) |
C21—N20—C16—N17 | 177.5 (1) | C13—C14—C15—C16 | −64.5 (2) |
C21—N20—C16—C15 | −6.4 (3) | C14—C15—C16—N17 | 80.6 (2) |
N19—N20—C21—C22 | −65.2 (2) | C14—C15—C16—N20 | −94.9 (2) |
N19—N20—C21—C26 | 59.4 (2) | N20—C21—C22—C23 | 177.0 (1) |
C16—N20—C21—C22 | 116.9 (2) | C26—C21—C22—C23 | 53.4 (2) |
C16—N20—C21—C26 | −118.5 (2) | N20—C21—C26—C25 | −176.8 (1) |
O2—C2—C3—C4 | −141.1 (2) | C22—C21—C26—C25 | −53.2 (2) |
N1—C2—C3—C4 | 40.4 (2) | C21—C22—C23—C24 | −55.3 (2) |
C2—C3—C4—C5 | −51.6 (2) | C22—C23—C24—C25 | 56.4 (2) |
C3—C4—C5—C6 | −149.8 (1) | C23—C24—C25—C26 | −56.1 (2) |
C3—C4—C5—C10 | 31.4 (2) | C24—C25—C26—C21 | 54.7 (2) |
Experimental details
(IA) | (IC) | |
Crystal data | ||
Chemical formula | C20H27N5O2 | C20H27N5O2 |
Mr | 369.47 | 369.47 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/n |
Temperature (K) | 294 | 294 |
a, b, c (Å) | 11.324 (1), 9.855 (1), 35.012 (1) | 5.148 (1), 10.739 (1), 35.279 (1) |
α, β, γ (°) | 90, 90, 90 | 90, 94.070 (1), 90 |
V (Å3) | 3907.3 (5) | 1945.3 (6) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.58 × 0.08 × 0.05 | 0.22 × 0.12 × 0.06 |
Data collection | ||
Diffractometer | 95mm CCD camera on κ goniostat diffractometer | 95mm CCD camera on κ-goniometer diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4045, 3548, 2341 | 4572, 4343, 2223 |
Rint | 0.028 | 0.026 |
(sin θ/λ)max (Å−1) | 0.603 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.042, 2.10 | 0.043, 0.041, 4.19 |
No. of reflections | 2540 | 2223 |
No. of parameters | 255 | 245 |
No. of restraints | 132 | 108 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.15 | 0.13, −0.12 |
Computer programs: KappaCCD Server Software (Nonius, 1997), KappaCCD Server Software, DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR (Burla et al., 1989), LSFM in OpenMolEN (Nonius, 1997), ORTEPII (Johnson, 1976), CIFGEN in OpenMolEN.
C12—O11—C7—C8 | −8.0 (2) | C12—C13—C14—C15 | 71.0 (2) |
C16—N20—C21—C22 | 97.2 (1) | C13—C14—C15—C16 | 179.7 (1) |
C16—N20—C21—C26 | −138.0 (1) | C14—C15—C16—N17 | 64.9 (2) |
O11—C12—C13—C14 | 174.7 (1) | C14—C15—C16—N20 | −111.7 (2) |
C12—O11—C7—C6 | −176.9 (1) | C12—C13—C14—C15 | 178.5 (1) |
C16—N20—C21—C22 | 116.9 (2) | C13—C14—C15—C16 | −64.5 (2) |
C16—N20—C21—C26 | −118.5 (2) | C14—C15—C16—N17 | 80.6 (2) |
O11—C12—C13—C14 | −174.7 (1) | C14—C15—C16—N20 | −94.9 (2) |
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6-[4-(1-Cyclohexyl-1H-tetrazol-5-yl)butoxy]-3,4-dihydroquinolin-2(1H)-one (cilostazol), (I), belongs to a class of compounds with proven activity as antithrombotic agents. Recently, two additional thermally produced crystalline polymorphic forms of this material were discovered, (IB) and (IC) (Stowell & Whittle, 2002; Stowell et al., 2002). Due to the poor solubility of the currently marketed active pharmaceutical ingredient, (IA), new polymorphs are of significant interest to the pharmaceutical industry, as they may have enhanced solubility, bioavailabilty, stability and other desirable characteristics. This paper presents the single-crystal analysis of (IA) and (IC). Suitable crystals of (IB) could not be isolated. To our knowledge, these are the first reported crystal structure determinations of (IA) and/or (IC). \sch
The present X-ray data allowed for the determination of the molecular conformation and packing for cilostazol, (IA) (Fig. 1). The structural data for (IC) (Fig. 2) showed distinct differences in the molecular conformation and packing diagrams compared with (IA). The bond lengths and angles for (IA) and (IC) are in accordance with anticipated values.
In (IA), the puckering parameters (Cremer & Pople, 1975) for the six-membered cyclohexyl ring (C21/C22/C23/C24/C25/C26) are q2 = 0.010 (2) Å, ϕ2 = 93.0 (95)° and θ = 1.0 (2)°. The latter value is close to zero, indicating a chair conformation of the ring. Puckering parameters for the quinolinone ring (N1/C2/C3/C4/C5/C10) are q2 = 0.395 (2) Å, ϕ2 = 146.2 (2)° and θ = 59.1 (2)°. The values for ϕ2 and θ indicate a skew boat conformation for this ring.
In (IC), the puckering parameters for the six-membered cyclohexyl ring (C21/C22/C23/C24/C25/C26) are q3 = 0.556 (2) Å, ϕ2 = 10.9 (46)° and θ = 1.4 (2)°. This matches the parameters for (IA), indicating that the rings in (IA) and (IC) share the same molecular conformation. The puckering parameters for the quinolinone ring (N1/C2/C3/C4/C5/C10) are q2 = 0.407 (2) Å, ϕ2 = 322.1 (2)° and θ = 64.2 (3)°. The values for ϕ2 and θ indicate a skew boat conformation for this ring, matching the conformation for (IA).
A comparison of the additional structural features of these two polymorphs reveals significant differences between them. A comparison of the torsion angles shows a twisting of the molecules, from atom O11 extending through to the cyclohexyl ring (Tables 1 and 2); additional geometric details are available in the archived CIFs. The O11—C12—C13—C14, C12—C13—C14—C15 and C14—C15—C16—N20 torsion angles demonstrate the most significant differences between the two polymorphs. Figs. 3 and 4 illustrate the unit-cell packing and show the differences between the packing of the two polymorphs.