organic compounds
2,6-Dichloro-9-(2′,3′,5′-tri-O-acetyl-β-D-ribofuranosyl)-9H-purine
aDepartment of Material Science and Applied Chemistry, Riga Technical University, 14/24 Azenes street, Riga, LV-1007, Latvia, and bLatvian Institute of Organic Synthesis, 21 Aizkraukles street, Riga, LV-1006, Latvia
*Correspondence e-mail: irina.novosjolova@rtu.lv
The title synthetic analog of purine 16H16Cl2N4O7, has its acetylated β-furanose ring in a 3′β-envelope conformation, with the corresponding C atom deviating by 0.602 (5) Å from the rest of the ring. The planar part of the furanose ring forms a dihedral angle of 65.0 (1)° with the mean plane of the purine bicycle. In the crystal, molecules form a three-dimensional network through multiple C—H⋯O and C—H⋯N hydrogen bonds and C—H⋯π interactions.
CCCDC reference: 968101
Related literature
For applications of 9-(2′,3′,5′-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine in synthesis, see: Caner & Vilarrasa (2010); Korboukh et al. (2012). For the synthesis, see: Vorbrüggen (1995); Robins & Uznański (1981); Nair & Richardson (1982); Francom et al. (2002); Francom & Robins (2003); Gerster & Robins (1966). The conditions were improved by using our previous studies (Kovalovs et al., 2013; Novosjolova et al., 2013). For the biological activity of purine their anticancer and antiviral activity and use as agonists and antagonists of adenosine receptors, see: Lech-Maranda et al. (2006); Robak et al. (2009); Gumina et al. (2003); Fredholm et al. (2011); Elzein & Zablocki (2008). For the structure of another 2,6-dichloropurine ribonucleoside, 9-(2′-deoxy-3′,5′-di-O-4-methoxybenzoyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine, see:Yang et al. (2012). The purine heterocycle is known to form π–π stacking interactions in related structures, see: Sternglanz & Bugg (1975). For standard bond lengths, see: Allen et al. (1987). The nature of hydrogen bonding is described by Gilli (2002). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
|
Data collection: KappaCCD Server Software (Nonius, 1997); cell SCALEPACK (Otwinovski & Minor, 1997); data reduction: DENZO (Otwinovski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 968101
10.1107/S1600536813034521/ld2116sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813034521/ld2116Isup2.hkl
Purine
are well known of their biological activity: anticancer and antiviral activities, and as agonists and antagonists of adenosine receptors (Lech-Maranda et al. (2006), Robak et al. (2009), Gumina et al. (2003), Fredholm et al. (2011), Elzein & Zablocki (2008).There is only one example of similar β-D-ribofuranosyl)-2,6-dichloro-9H-purine) in literature (Yang et al., 2012, CSD refcode KEBWOF). Search of the Cambridge Structural Database (CSD, Version 1.15; Allen, 2002) indicated that there are only 4 (CSD refcodes: CLPURB, JEMHUF, PUPZAC, ZEXWEE) entries of 2- or 6-chloro substituted derivatives from over 300 crystal structures of 9-(ribofuranosyl)-9H-purines. The bond lengths (Allen et al., 1987) and angles in the molecule of are close to standard values. The furanose cycle adopts an Atoms C2', C1', O6' and C4' of furanose lie in same plane (denoted as plane A), 2'- and 5'-O-acetyl groups are on opposite sides of the A plane, while 3'-O-acetyl group lies close to the A plane. The C3' deviates from the A by 0.602 (5) Å. The dihedral angle between the least-square planes of the purine system and four planar atoms (C2', C1', O6' and C4') of furanose cycle is 65.0 (1)°. The main torsion angles describing the location of purine system in respect to furanose ring are: C8—N9—C1'—O6' (6.9 (4)°); C8—N9—C1'—C2' (-111.1 (3)°); C4—N9—C1'—O6' (-168.8 (3)°); C4—N9—C1'—C2' (73.2 (4)°). Regardless of the fact that purine heterocycle is known to form π–π stacking interactions in related structures (Sternglanz & Bugg, 1975), such interaction was not observed in the crystals of the title compound. Moderate hydrogen bonds type C—H···O and C— H···N are present to form and stabilize three-dimensional architecture (Table 1).
of 2,6-dichloropurine ribonucleoside (9-(2'-deoxy-3',5'-di-O-4-methoxybenzoyl-The 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine 1 was synthesized by method of Vorbrüggen glycosylation of 2,6-dichloropurine (Vorbrüggen, 1995). The conditions were improved by using our previous studies (Kovalovs et al., 2013; Novosjolova et al., 2013).
Single crystals of 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine were grown from an ethanol solution by slow evaporation in ambient temperature. 1H-NMR and 13C-NMR spectra were recorded at 300 MHz and at 75.5 MHz, respectively. The proton signals for residual non-deuterated solvents (δ 7.26 for CDCl3) and carbon signals (δ 77.1 for CDCl3) were used as an internal references for 1H-NMR and 13C-NMR spectra, respectively. Coupling constants are reported in Hz. Analytical thin layer (TLC) was performed on Kieselgel 60 F254 glass plates precoated with a 0.25 mm thickness of silica gel. Dry MeCN was obtained by distillation over CaH2. Commercial reagents were used as received.
9-(2',3',5'-Tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine (3). N,O-Bis(trimethylsilyl)acetamide (5.60 mL, 22.7 mmol) was added to a stirred suspension of 2,6-dichloropurine (2) (4.02 g, 21.2 mmol) in dry acetonitrile (50 mL). The resulting mixture was stirred at 40 °C for 30 min until a clear solution was obtained. Solution of tetra-O-acetyl-D-ribofuranose (1) (6.77 g, 21.3 mmol) in dry acetonitrile (35 mL) was then added, followed by TMSOTf (0.80 mL, 4.4 mmol). The resulting reaction mixture was stirred at 75-80 °C for 2.5-3 h (TLC control). Then it was cooled to ambient temperature and ethanol (1 mL) was added and the mixture was stirred for 15 min at the same temperature followed by evaporation under reduced pressure. The residue was dissolved in CH2Cl2 (100 mL) washed with saturated aqueous solution of NaHCO3 (3 × 25 mL) and water (1 × 25 mL), dried over anh. Na2SO4. Evaporation under reduced pressure provided product 3 (8.95 g, 95%) as a slightly yellow powder. The title compound was crystallized from ethanol, mp 158-160 °C [lit.: 159-161 °C (Gerster & Robins, 1966)]. The other analytical data of 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine are consistent with those reported earlier (Francom et al., 2002; Caner & Vilarrasa, 2010). Rf=0.45 (Toluene/EtOAc 1:2), IR (KBr), ν, cm-1: 2976, 2924, 1773, 1742, 1593, 1560, 1381, 1367, 1245, 1229, 1200, 1137, 1100, 1061; 1H-NMR (300 MHz, CDCl3) δ (ppm): 8.29 (s, 1H, H—C(8)), 6.21 (d, 1H, 3J1'-2' = 5.6 Hz, H—C(1')), 5.79 (t, 1H, 3J1'-2' = 3J2'-3' = 5.6 Hz, H—C(2')), 5.57 (dd, 1H, 3J2'-3' = 5.6 Hz, 3J3'-4' = 4.4 Hz, H—C(3')), 4.47 (quartet, 1H, 3J3'-4' = 3J4'-5' = 4.4 Hz, H—C(4')), 4.41 (d, 2H, 3J4'-5' = 4.4 Hz, H—C(5')), 2.16, 2.14, 2.09 (3s, 9H, H3COOC-C(2',3',5')); 13C-NMR (75.5 MHz, CDCl3) δ (ppm): 170.2, 169.5, 169.4, 153.3, 152.6, 152.2, 143.9, 131.3, 86.5, 80.8, 73.2, 70.5, 62.8, 20.7, 20.5, 20.3.
Crystal data, data collection and structure
details are summarized in Table 1. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were positioned geometrically with C—H distances ranging from 0.93 Å to 0.98 Å and refined as riding on their parent atoms with Uiso (H) = 1.5Ueq (C) for methyl groups and Uiso (H) = 1.2Ueq (C) for others.Purine
are well known of their biological activity: anticancer and antiviral activities, and as agonists and antagonists of adenosine receptors (Lech-Maranda et al. (2006), Robak et al. (2009), Gumina et al. (2003), Fredholm et al. (2011), Elzein & Zablocki (2008).There is only one example of similar β-D-ribofuranosyl)-2,6-dichloro-9H-purine) in literature (Yang et al., 2012, CSD refcode KEBWOF). Search of the Cambridge Structural Database (CSD, Version 1.15; Allen, 2002) indicated that there are only 4 (CSD refcodes: CLPURB, JEMHUF, PUPZAC, ZEXWEE) entries of 2- or 6-chloro substituted derivatives from over 300 crystal structures of 9-(ribofuranosyl)-9H-purines. The bond lengths (Allen et al., 1987) and angles in the molecule of are close to standard values. The furanose cycle adopts an Atoms C2', C1', O6' and C4' of furanose lie in same plane (denoted as plane A), 2'- and 5'-O-acetyl groups are on opposite sides of the A plane, while 3'-O-acetyl group lies close to the A plane. The C3' deviates from the A by 0.602 (5) Å. The dihedral angle between the least-square planes of the purine system and four planar atoms (C2', C1', O6' and C4') of furanose cycle is 65.0 (1)°. The main torsion angles describing the location of purine system in respect to furanose ring are: C8—N9—C1'—O6' (6.9 (4)°); C8—N9—C1'—C2' (-111.1 (3)°); C4—N9—C1'—O6' (-168.8 (3)°); C4—N9—C1'—C2' (73.2 (4)°). Regardless of the fact that purine heterocycle is known to form π–π stacking interactions in related structures (Sternglanz & Bugg, 1975), such interaction was not observed in the crystals of the title compound. Moderate hydrogen bonds type C—H···O and C— H···N are present to form and stabilize three-dimensional architecture (Table 1).
of 2,6-dichloropurine ribonucleoside (9-(2'-deoxy-3',5'-di-O-4-methoxybenzoyl-The 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine 1 was synthesized by method of Vorbrüggen glycosylation of 2,6-dichloropurine (Vorbrüggen, 1995). The conditions were improved by using our previous studies (Kovalovs et al., 2013; Novosjolova et al., 2013).
Single crystals of 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine were grown from an ethanol solution by slow evaporation in ambient temperature. 1H-NMR and 13C-NMR spectra were recorded at 300 MHz and at 75.5 MHz, respectively. The proton signals for residual non-deuterated solvents (δ 7.26 for CDCl3) and carbon signals (δ 77.1 for CDCl3) were used as an internal references for 1H-NMR and 13C-NMR spectra, respectively. Coupling constants are reported in Hz. Analytical thin layer (TLC) was performed on Kieselgel 60 F254 glass plates precoated with a 0.25 mm thickness of silica gel. Dry MeCN was obtained by distillation over CaH2. Commercial reagents were used as received.
9-(2',3',5'-Tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine (3). N,O-Bis(trimethylsilyl)acetamide (5.60 mL, 22.7 mmol) was added to a stirred suspension of 2,6-dichloropurine (2) (4.02 g, 21.2 mmol) in dry acetonitrile (50 mL). The resulting mixture was stirred at 40 °C for 30 min until a clear solution was obtained. Solution of tetra-O-acetyl-D-ribofuranose (1) (6.77 g, 21.3 mmol) in dry acetonitrile (35 mL) was then added, followed by TMSOTf (0.80 mL, 4.4 mmol). The resulting reaction mixture was stirred at 75-80 °C for 2.5-3 h (TLC control). Then it was cooled to ambient temperature and ethanol (1 mL) was added and the mixture was stirred for 15 min at the same temperature followed by evaporation under reduced pressure. The residue was dissolved in CH2Cl2 (100 mL) washed with saturated aqueous solution of NaHCO3 (3 × 25 mL) and water (1 × 25 mL), dried over anh. Na2SO4. Evaporation under reduced pressure provided product 3 (8.95 g, 95%) as a slightly yellow powder. The title compound was crystallized from ethanol, mp 158-160 °C [lit.: 159-161 °C (Gerster & Robins, 1966)]. The other analytical data of 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine are consistent with those reported earlier (Francom et al., 2002; Caner & Vilarrasa, 2010). Rf=0.45 (Toluene/EtOAc 1:2), IR (KBr), ν, cm-1: 2976, 2924, 1773, 1742, 1593, 1560, 1381, 1367, 1245, 1229, 1200, 1137, 1100, 1061; 1H-NMR (300 MHz, CDCl3) δ (ppm): 8.29 (s, 1H, H—C(8)), 6.21 (d, 1H, 3J1'-2' = 5.6 Hz, H—C(1')), 5.79 (t, 1H, 3J1'-2' = 3J2'-3' = 5.6 Hz, H—C(2')), 5.57 (dd, 1H, 3J2'-3' = 5.6 Hz, 3J3'-4' = 4.4 Hz, H—C(3')), 4.47 (quartet, 1H, 3J3'-4' = 3J4'-5' = 4.4 Hz, H—C(4')), 4.41 (d, 2H, 3J4'-5' = 4.4 Hz, H—C(5')), 2.16, 2.14, 2.09 (3s, 9H, H3COOC-C(2',3',5')); 13C-NMR (75.5 MHz, CDCl3) δ (ppm): 170.2, 169.5, 169.4, 153.3, 152.6, 152.2, 143.9, 131.3, 86.5, 80.8, 73.2, 70.5, 62.8, 20.7, 20.5, 20.3.
For applications of 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine in synthesis, see: Caner & Vilarrasa (2010); Korboukh et al. (2012). For the synthesis, see: Vorbrüggen (1995); Robins & Uznański (1981); Nair & Richardson (1982); Francom et al. (2002); Francom & Robins (2003); Gerster & Robins (1966). The conditions were improved by using our previous studies (Kovalovs et al., 2013; Novosjolova et al., 2013). For the biological activity of purine their anticancer and antiviral activity and use as agonists and antagonists of adenosine receptors, see: Lech-Maranda et al. (2006); Robak et al. (2009); Gumina et al. (2003); Fredholm et al. (2011); Elzein & Zablocki (2008). For the structure of another 2,6-dichloropurine ribonucleoside, 9-(2'-deoxy-3',5'-di-O-4-methoxybenzoyl-β-D-ribofuranosyl)-2,6-dichloro-9H-purine, see:Yang et al. (2012). The purine heterocycle is known to form π–π stacking interactions in related structures, see: Sternglanz & Bugg (1975). For standard bond lengths, see: Allen et al. (1987). The nature of hydrogen bonding is described by Gilli (2002). For a description of the Cambridge Structural Database, see: Allen (2002).
detailsCrystal data, data collection and structure
details are summarized in Table 1. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were positioned geometrically with C—H distances ranging from 0.93 Å to 0.98 Å and refined as riding on their parent atoms with Uiso (H) = 1.5Ueq (C) for methyl groups and Uiso (H) = 1.2Ueq (C) for others.Data collection: KappaCCD Server Software (Nonius, 1997); cell
SCALEPACK (Otwinovski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinovski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).Fig. 1. The asymmetric unit of the title compound showing 50% probability displacement ellipsoids and the atom-numbering (hydrogen atoms are shown as small spheres of arbitrary radii) | |
Fig. 2. Packing diagram of the title compound viewed down the b axis |
C16H16Cl2N4O7 | F(000) = 460 |
Mr = 447.23 | Dx = 1.497 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 17407 reflections |
a = 10.1324 (2) Å | θ = 1.0–27.5° |
b = 9.6887 (3) Å | µ = 0.37 mm−1 |
c = 10.5399 (2) Å | T = 296 K |
β = 106.537 (2)° | Prism, colorless |
V = 991.90 (4) Å3 | 0.38 × 0.32 × 0.15 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 2846 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
CCD scans | h = −13→13 |
3898 measured reflections | k = −11→12 |
3898 independent reflections | l = −13→13 |
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0352P)2 + 0.3514P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3898 reflections | Δρmax = 0.22 e Å−3 |
265 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1518 Friedel pairs |
0 constraints | Absolute structure parameter: 0.00 (7) |
Primary atom site location: structure-invariant direct methods |
C16H16Cl2N4O7 | V = 991.90 (4) Å3 |
Mr = 447.23 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.1324 (2) Å | µ = 0.37 mm−1 |
b = 9.6887 (3) Å | T = 296 K |
c = 10.5399 (2) Å | 0.38 × 0.32 × 0.15 mm |
β = 106.537 (2)° |
Nonius KappaCCD diffractometer | 2846 reflections with I > 2σ(I) |
3898 measured reflections | Rint = 0.000 |
3898 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.107 | Δρmax = 0.22 e Å−3 |
S = 1.02 | Δρmin = −0.20 e Å−3 |
3898 reflections | Absolute structure: Flack (1983), 1518 Friedel pairs |
265 parameters | Absolute structure parameter: 0.00 (7) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 1.0850 (3) | 0.1139 (3) | 0.4785 (3) | 0.0535 (8) | |
C2 | 0.9650 (4) | 0.1787 (4) | 0.4602 (3) | 0.0508 (9) | |
N3 | 0.9178 (3) | 0.2553 (3) | 0.5399 (2) | 0.0458 (6) | |
C4 | 1.0170 (3) | 0.2704 (3) | 0.6574 (3) | 0.0404 (7) | |
C5 | 1.1477 (3) | 0.2135 (4) | 0.6915 (3) | 0.0429 (8) | |
C6 | 1.1761 (4) | 0.1309 (4) | 0.5952 (3) | 0.0510 (9) | |
N7 | 1.2211 (3) | 0.2508 (3) | 0.8196 (3) | 0.0506 (7) | |
C8 | 1.1331 (3) | 0.3266 (4) | 0.8596 (3) | 0.0473 (8) | |
H8 | 1.1540 | 0.3671 | 0.9430 | 0.057* | |
N9 | 1.0071 (2) | 0.3404 (3) | 0.7669 (2) | 0.0405 (6) | |
Cl10 | 1.32958 (12) | 0.04548 (15) | 0.62312 (11) | 0.0892 (4) | |
Cl11 | 0.85038 (11) | 0.15549 (12) | 0.30379 (9) | 0.0733 (3) | |
C1' | 0.8877 (3) | 0.4205 (4) | 0.7769 (3) | 0.0409 (7) | |
H1 | 0.8574 | 0.4827 | 0.7008 | 0.049* | |
C2' | 0.7695 (3) | 0.3282 (4) | 0.7845 (3) | 0.0397 (7) | |
H2 | 0.7642 | 0.2421 | 0.7344 | 0.048* | |
C3' | 0.8034 (3) | 0.3062 (3) | 0.9343 (3) | 0.0385 (7) | |
H3 | 0.8772 | 0.2380 | 0.9639 | 0.046* | |
C4' | 0.8537 (3) | 0.4472 (3) | 0.9862 (3) | 0.0382 (7) | |
H4 | 0.7733 | 0.5063 | 0.9786 | 0.046* | |
C5' | 0.9455 (3) | 0.4570 (4) | 1.1251 (3) | 0.0432 (8) | |
H5A | 0.9788 | 0.5509 | 1.1437 | 0.052* | |
H5B | 0.8946 | 0.4325 | 1.1870 | 0.052* | |
O6' | 0.9264 (2) | 0.4982 (2) | 0.89486 (18) | 0.0402 (5) | |
O7' | 0.6460 (2) | 0.4081 (2) | 0.74576 (19) | 0.0490 (6) | |
C8' | 0.5479 (3) | 0.3728 (4) | 0.6337 (3) | 0.0520 (9) | |
C9' | 0.4297 (4) | 0.4704 (5) | 0.6096 (4) | 0.0696 (12) | |
H9A | 0.4616 | 0.5627 | 0.6031 | 0.104* | |
H9C | 0.3895 | 0.4651 | 0.6816 | 0.104* | |
H9B | 0.3620 | 0.4462 | 0.5285 | 0.104* | |
O10' | 0.5636 (3) | 0.2809 (4) | 0.5649 (3) | 0.0967 (11) | |
O11' | 0.6883 (2) | 0.2701 (2) | 0.9804 (2) | 0.0458 (6) | |
C12' | 0.6474 (4) | 0.1370 (4) | 0.9636 (3) | 0.0504 (9) | |
C13' | 0.5286 (4) | 0.1098 (5) | 1.0189 (5) | 0.0826 (15) | |
H13A | 0.5188 | 0.0122 | 1.0288 | 0.124* | |
H13B | 0.4456 | 0.1462 | 0.9597 | 0.124* | |
H13C | 0.5455 | 0.1538 | 1.1037 | 0.124* | |
O14' | 0.7012 (3) | 0.0544 (3) | 0.9110 (3) | 0.0775 (8) | |
O15' | 1.0599 (2) | 0.3644 (2) | 1.13994 (18) | 0.0441 (5) | |
C16' | 1.1551 (3) | 0.3677 (4) | 1.2595 (3) | 0.0499 (8) | |
C17' | 1.2746 (4) | 0.2794 (4) | 1.2628 (3) | 0.0618 (10) | |
H17A | 1.3570 | 0.3342 | 1.2865 | 0.093* | |
H17B | 1.2630 | 0.2393 | 1.1770 | 0.093* | |
H17C | 1.2816 | 0.2075 | 1.3270 | 0.093* | |
O18' | 1.1385 (3) | 0.4370 (4) | 1.3478 (2) | 0.0909 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.063 (2) | 0.055 (2) | 0.0498 (17) | 0.0015 (15) | 0.0270 (14) | −0.0050 (14) |
C2 | 0.064 (2) | 0.052 (2) | 0.0376 (17) | −0.0083 (19) | 0.0173 (14) | −0.0028 (16) |
N3 | 0.0551 (17) | 0.0437 (17) | 0.0444 (15) | 0.0010 (13) | 0.0239 (12) | 0.0023 (13) |
C4 | 0.0511 (19) | 0.0378 (19) | 0.0362 (16) | −0.0014 (15) | 0.0189 (13) | 0.0051 (14) |
C5 | 0.0451 (19) | 0.046 (2) | 0.0406 (16) | 0.0016 (15) | 0.0166 (13) | 0.0040 (15) |
C6 | 0.057 (2) | 0.050 (2) | 0.0533 (19) | 0.0053 (17) | 0.0275 (16) | 0.0000 (17) |
N7 | 0.0465 (16) | 0.0552 (19) | 0.0495 (15) | 0.0014 (14) | 0.0126 (12) | −0.0009 (14) |
C8 | 0.050 (2) | 0.048 (2) | 0.0437 (17) | −0.0015 (16) | 0.0143 (14) | −0.0012 (15) |
N9 | 0.0450 (15) | 0.0425 (16) | 0.0363 (13) | 0.0033 (12) | 0.0154 (11) | 0.0016 (12) |
Cl10 | 0.0712 (7) | 0.1099 (11) | 0.0907 (7) | 0.0324 (7) | 0.0299 (6) | −0.0156 (7) |
Cl11 | 0.0824 (7) | 0.0903 (9) | 0.0433 (5) | −0.0046 (6) | 0.0118 (4) | −0.0139 (5) |
C1' | 0.0501 (18) | 0.0420 (19) | 0.0319 (14) | 0.0100 (15) | 0.0137 (12) | 0.0040 (14) |
C2' | 0.0413 (17) | 0.0406 (19) | 0.0364 (15) | 0.0043 (14) | 0.0096 (12) | −0.0049 (14) |
C3' | 0.0383 (16) | 0.0419 (19) | 0.0366 (15) | 0.0032 (14) | 0.0130 (12) | −0.0013 (14) |
C4' | 0.0405 (16) | 0.0397 (19) | 0.0357 (14) | 0.0054 (14) | 0.0129 (12) | −0.0043 (14) |
C5' | 0.0492 (18) | 0.044 (2) | 0.0364 (15) | 0.0030 (15) | 0.0116 (13) | −0.0055 (14) |
O6' | 0.0493 (12) | 0.0367 (13) | 0.0371 (11) | −0.0013 (10) | 0.0162 (9) | −0.0035 (9) |
O7' | 0.0426 (12) | 0.0597 (17) | 0.0380 (11) | 0.0133 (11) | 0.0005 (9) | −0.0104 (10) |
C8' | 0.044 (2) | 0.060 (3) | 0.0451 (18) | −0.0044 (17) | 0.0028 (14) | −0.0038 (18) |
C9' | 0.047 (2) | 0.084 (3) | 0.065 (2) | 0.011 (2) | −0.0044 (16) | −0.006 (2) |
O10' | 0.079 (2) | 0.096 (3) | 0.089 (2) | 0.0098 (18) | −0.0174 (16) | −0.048 (2) |
O11' | 0.0382 (12) | 0.0531 (16) | 0.0492 (12) | −0.0009 (11) | 0.0174 (9) | 0.0004 (11) |
C12' | 0.044 (2) | 0.054 (2) | 0.0484 (18) | −0.0001 (18) | 0.0050 (14) | 0.0148 (18) |
C13' | 0.053 (3) | 0.109 (4) | 0.087 (3) | −0.016 (2) | 0.022 (2) | 0.027 (3) |
O14' | 0.0762 (19) | 0.0504 (18) | 0.112 (2) | −0.0012 (16) | 0.0364 (17) | 0.0004 (17) |
O15' | 0.0455 (12) | 0.0469 (14) | 0.0356 (10) | 0.0033 (10) | 0.0049 (9) | −0.0040 (10) |
C16' | 0.051 (2) | 0.048 (2) | 0.0401 (18) | −0.0036 (17) | −0.0029 (14) | −0.0044 (17) |
C17' | 0.056 (2) | 0.062 (3) | 0.057 (2) | 0.006 (2) | 0.0006 (16) | 0.0030 (19) |
O18' | 0.087 (2) | 0.120 (3) | 0.0482 (14) | 0.026 (2) | −0.0101 (13) | −0.0346 (18) |
N1—C6 | 1.321 (4) | C4'—C5' | 1.497 (4) |
N1—C2 | 1.333 (4) | C4'—H4 | 0.9800 |
C2—N3 | 1.308 (4) | C5'—O15' | 1.439 (4) |
C2—Cl11 | 1.740 (3) | C5'—H5A | 0.9700 |
N3—C4 | 1.363 (4) | C5'—H5B | 0.9700 |
C4—N9 | 1.367 (4) | O7'—C8' | 1.354 (4) |
C4—C5 | 1.384 (4) | C8'—O10' | 1.187 (4) |
C5—C6 | 1.386 (4) | C8'—C9' | 1.489 (5) |
C5—N7 | 1.391 (4) | C9'—H9A | 0.9600 |
C6—Cl10 | 1.712 (4) | C9'—H9C | 0.9600 |
N7—C8 | 1.314 (4) | C9'—H9B | 0.9600 |
C8—N9 | 1.376 (4) | O11'—C12' | 1.351 (5) |
C8—H8 | 0.9300 | C12'—O14' | 1.190 (4) |
N9—C1' | 1.466 (4) | C12'—C13' | 1.502 (5) |
C1'—O6' | 1.409 (4) | C13'—H13A | 0.9600 |
C1'—C2' | 1.515 (5) | C13'—H13B | 0.9600 |
C1'—H1 | 0.9800 | C13'—H13C | 0.9600 |
C2'—O7' | 1.429 (4) | O15'—C16' | 1.352 (3) |
C2'—C3' | 1.532 (4) | C16'—O18' | 1.198 (4) |
C2'—H2 | 0.9800 | C16'—C17' | 1.475 (5) |
C3'—O11' | 1.429 (3) | C17'—H17A | 0.9600 |
C3'—C4' | 1.505 (5) | C17'—H17B | 0.9600 |
C3'—H3 | 0.9800 | C17'—H17C | 0.9600 |
C4'—O6' | 1.455 (3) | ||
C6—N1—C2 | 116.3 (3) | C5'—C4'—C3' | 117.7 (3) |
N3—C2—N1 | 131.2 (3) | O6'—C4'—H4 | 108.3 |
N3—C2—Cl11 | 114.5 (3) | C5'—C4'—H4 | 108.3 |
N1—C2—Cl11 | 114.3 (2) | C3'—C4'—H4 | 108.3 |
C2—N3—C4 | 109.5 (3) | O15'—C5'—C4' | 108.9 (2) |
N3—C4—N9 | 127.5 (3) | O15'—C5'—H5A | 109.9 |
N3—C4—C5 | 126.6 (3) | C4'—C5'—H5A | 109.9 |
N9—C4—C5 | 105.9 (3) | O15'—C5'—H5B | 109.9 |
C4—C5—C6 | 115.0 (3) | C4'—C5'—H5B | 109.9 |
C4—C5—N7 | 110.9 (3) | H5A—C5'—H5B | 108.3 |
C6—C5—N7 | 134.1 (3) | C1'—O6'—C4' | 109.7 (2) |
N1—C6—C5 | 121.2 (3) | C8'—O7'—C2' | 118.5 (3) |
N1—C6—Cl10 | 117.4 (2) | O10'—C8'—O7' | 122.0 (3) |
C5—C6—Cl10 | 121.4 (3) | O10'—C8'—C9' | 127.8 (3) |
C8—N7—C5 | 103.5 (3) | O7'—C8'—C9' | 110.1 (3) |
N7—C8—N9 | 113.8 (3) | C8'—C9'—H9A | 109.5 |
N7—C8—H8 | 123.1 | C8'—C9'—H9C | 109.5 |
N9—C8—H8 | 123.1 | H9A—C9'—H9C | 109.5 |
C4—N9—C8 | 105.9 (3) | C8'—C9'—H9B | 109.5 |
C4—N9—C1' | 125.7 (2) | H9A—C9'—H9B | 109.5 |
C8—N9—C1' | 128.2 (3) | H9C—C9'—H9B | 109.5 |
O6'—C1'—N9 | 108.5 (2) | C12'—O11'—C3' | 116.1 (3) |
O6'—C1'—C2' | 107.2 (2) | O14'—C12'—O11' | 122.6 (3) |
N9—C1'—C2' | 111.8 (3) | O14'—C12'—C13' | 126.0 (4) |
O6'—C1'—H1 | 109.8 | O11'—C12'—C13' | 111.5 (4) |
N9—C1'—H1 | 109.8 | C12'—C13'—H13A | 109.5 |
C2'—C1'—H1 | 109.8 | C12'—C13'—H13B | 109.5 |
O7'—C2'—C1' | 107.8 (3) | H13A—C13'—H13B | 109.5 |
O7'—C2'—C3' | 106.9 (2) | C12'—C13'—H13C | 109.5 |
C1'—C2'—C3' | 100.8 (2) | H13A—C13'—H13C | 109.5 |
O7'—C2'—H2 | 113.5 | H13B—C13'—H13C | 109.5 |
C1'—C2'—H2 | 113.5 | C16'—O15'—C5' | 115.2 (2) |
C3'—C2'—H2 | 113.5 | O18'—C16'—O15' | 121.1 (3) |
O11'—C3'—C4' | 108.8 (2) | O18'—C16'—C17' | 127.1 (3) |
O11'—C3'—C2' | 114.8 (2) | O15'—C16'—C17' | 111.8 (3) |
C4'—C3'—C2' | 101.7 (2) | C16'—C17'—H17A | 109.5 |
O11'—C3'—H3 | 110.4 | C16'—C17'—H17B | 109.5 |
C4'—C3'—H3 | 110.4 | H17A—C17'—H17B | 109.5 |
C2'—C3'—H3 | 110.4 | C16'—C17'—H17C | 109.5 |
O6'—C4'—C5' | 109.5 (2) | H17A—C17'—H17C | 109.5 |
O6'—C4'—C3' | 104.5 (2) | H17B—C17'—H17C | 109.5 |
C6—N1—C2—N3 | −2.3 (6) | O6'—C1'—C2'—O7' | 82.0 (3) |
C6—N1—C2—Cl11 | 178.7 (3) | N9—C1'—C2'—O7' | −159.2 (2) |
N1—C2—N3—C4 | 3.0 (5) | O6'—C1'—C2'—C3' | −29.8 (3) |
Cl11—C2—N3—C4 | −178.0 (2) | N9—C1'—C2'—C3' | 89.0 (3) |
C2—N3—C4—N9 | −178.6 (3) | O7'—C2'—C3'—O11' | 44.0 (4) |
C2—N3—C4—C5 | −0.9 (5) | C1'—C2'—C3'—O11' | 156.5 (3) |
N3—C4—C5—C6 | −1.5 (5) | O7'—C2'—C3'—C4' | −73.3 (3) |
N9—C4—C5—C6 | 176.6 (3) | C1'—C2'—C3'—C4' | 39.2 (3) |
N3—C4—C5—N7 | 180.0 (3) | O11'—C3'—C4'—O6' | −157.0 (2) |
N9—C4—C5—N7 | −1.9 (4) | C2'—C3'—C4'—O6' | −35.5 (3) |
C2—N1—C6—C5 | −0.8 (5) | O11'—C3'—C4'—C5' | 81.3 (3) |
C2—N1—C6—Cl10 | 178.4 (3) | C2'—C3'—C4'—C5' | −157.2 (2) |
C4—C5—C6—N1 | 2.4 (5) | O6'—C4'—C5'—O15' | −65.6 (3) |
N7—C5—C6—N1 | −179.6 (4) | C3'—C4'—C5'—O15' | 53.4 (3) |
C4—C5—C6—Cl10 | −176.8 (3) | N9—C1'—O6'—C4' | −112.7 (3) |
N7—C5—C6—Cl10 | 1.2 (6) | C2'—C1'—O6'—C4' | 8.2 (3) |
C4—C5—N7—C8 | 0.9 (4) | C5'—C4'—O6'—C1' | 144.5 (2) |
C6—C5—N7—C8 | −177.2 (4) | C3'—C4'—O6'—C1' | 17.6 (3) |
C5—N7—C8—N9 | 0.4 (4) | C1'—C2'—O7'—C8' | 115.0 (3) |
N3—C4—N9—C8 | −179.9 (3) | C3'—C2'—O7'—C8' | −137.4 (3) |
C5—C4—N9—C8 | 2.0 (3) | C2'—O7'—C8'—O10' | −2.6 (5) |
N3—C4—N9—C1' | −3.4 (5) | C2'—O7'—C8'—C9' | −178.7 (3) |
C5—C4—N9—C1' | 178.5 (3) | C4'—C3'—O11'—C12' | −168.0 (2) |
N7—C8—N9—C4 | −1.6 (4) | C2'—C3'—O11'—C12' | 78.9 (3) |
N7—C8—N9—C1' | −177.9 (3) | C3'—O11'—C12'—O14' | −1.6 (5) |
C4—N9—C1'—O6' | −168.8 (3) | C3'—O11'—C12'—C13' | 178.4 (3) |
C8—N9—C1'—O6' | 6.9 (4) | C4'—C5'—O15'—C16' | 176.9 (3) |
C4—N9—C1'—C2' | 73.2 (4) | C5'—O15'—C16'—O18' | 4.7 (5) |
C8—N9—C1'—C2' | −111.1 (3) | C5'—O15'—C16'—C17' | −174.8 (3) |
Cg is the centroid of the C4/C5/N7/C8/N9 imidazole ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O15′ | 0.93 | 2.52 | 3.265 (4) | 137 |
C8—H8···O14′i | 0.93 | 2.56 | 3.350 (4) | 143 |
C1′—H1···N1ii | 0.98 | 2.48 | 3.355 (5) | 148 |
C9′—H9B···O18′iii | 0.96 | 2.51 | 3.434 (4) | 161 |
C13′—H13B···N7iv | 0.96 | 2.54 | 3.502 (5) | 175 |
C5′—H5A···Cgi | 0.97 | 2.69 | 3.454 | 136 |
Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) −x+2, y+1/2, −z+1; (iii) x−1, y, z−1; (iv) x−1, y, z. |
Cg is the centroid of the C4/C5/N7/C8/N9 imidazole ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O15' | 0.93 | 2.52 | 3.265 (4) | 137 |
C8—H8···O14'i | 0.93 | 2.56 | 3.350 (4) | 143 |
C1'—H1···N1ii | 0.98 | 2.48 | 3.355 (5) | 148 |
C9'—H9B···O18'iii | 0.96 | 2.51 | 3.434 (4) | 161 |
C13'—H13B···N7iv | 0.96 | 2.54 | 3.502 (5) | 175 |
C5'—H5A···Cgi | 0.97 | 2.69 | 3.454 | 136 |
Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) −x+2, y+1/2, −z+1; (iii) x−1, y, z−1; (iv) x−1, y, z. |
Acknowledgements
IN thanks the European Social Fund within the project `Support for the implementation of doctoral studies at Riga Technical University' for a scholarship and ERDF project 2DP/2.1.1.2.0/10/APIA/VI4AA/003 for the opportunity to present this work at the 14th Tetrahedron Symposium.
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