research communications
of 5-(dibenzofuran-4-yl)-2′-deoxyuridine
aDepartment of Chemistry, Institute of Chemical Technology, Nathalal Parekh Road, Matunga, Mumbai 400 019, India, and bInstitut für Biochemie, Ernst-Moritz-Arndt Universität Greifswald, Felix-Hausdorff-Strasse 4, D-17487 Greifswald, Germany
*Correspondence e-mail: carola.schulzke@uni-greifswald.de
The molecule of the title compound, C21H18N2O6, has a bent rather than a linear conformation supported by three intramolecular C—H⋯O hydrogen bonds. The packing in the is largely determined by interactions between hydrogen atoms with oxygen atom lone pairs with one molecule interacting with neigbouring molecules via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds. The title compound crystallizes in the chiral orthorhombic P212121. Its could not be determined crystallographically and was assumed with reference to that of the reactant 5-iodo-2′-deoxyuridine.
Keywords: nucleoside; palladium; catalysis; uridine; Suzuki-Miyaura cross-coupling; crystal structure.
CCDC reference: 1574284
1. Chemical context
As a result of their numerous applications, synthetically modified nucleoside analogues have attracted much attention in recent years. Many of these modified etc (Huryn & Okabe, 1992). Modern trends in this field of research consider palladium complexes to be active catalysts for the efficient modification of because of their greater ability to perform such catalytic processes in aqueous media (Agrofoglio et al., 2003; Kapdi et al., 2014). Base modification in purine and pyrimidine resulting in a new class of compounds with better fluorescence properties, enhancing their chances of being employed as biological probes for studying biological environments such as DNA damage, protein–DNA interactions and DNA probes is of great interest to chemical biologists as well as bio-organic chemists (Tanpure et al., 2013). Structural elucidation of such compounds is an important task in order to understand the mechanistic pathways. Herein we present the synthesis and the of the title compound, 5-(dibenzofuran-4-yl)-2′-deoxyuridine.
show potential activity as drug candidates, biological probes2. Structural commentary
The title compound crystallizes in the orthorhombic P212121 with four molecules in the The two aromatic π systems (pyrimidine and dibenzofuranyl), which are connected by a C—C bond [C7—C10 = 1.489 (6) Å] subtend a dihedral angle of 30.7 (2)° (Fig. 1). All bond lengths or angles are comparable to those in related compounds. Fifty two entries can be found in the Cambridge Crystallographic Database (ConQuest Version 1.19; Groom et al., 2016) for deoxyuridine with a substituent only in the C5 position of the base (i.e. C7 here) and neither substituents nor protecting groups anywhere else, nine of which are for compounds that had already been characterized (i.e. repeats, polymorphs, present/absent solvent). The bond lengths of the pyrimidine moiety observed for the title compound are very close to the average values found for related structures (see Table S1 in the Supporting information). As is typical for this class of compounds, the bond usually assigned to be a double bond within the six-membered ring (here C6=C7) is the shortest for the pyrimidine ring at 1.353 (6) Å and the bond between the second carbonyl carbon atom and the substituted carbon (here C7—C8) is the longest at 1.447 (6) Å. All four other ring atom-to-ring atom distances (N—C and C—C bonds) are shorter than 1.393 Å, indicating significant π-electron delocalization throughout the pyrimidine base. All this, however, is in accordance with the majority of previously reported structures.
The relative orientation between sugar and base moieties in the title compound is also comparable with compounds in the database. The hydrogen-bonding interaction (or distance) between the C6-H function (here C6) and the ring oxygen atom of the sugar (here O3) and/or the –CH3–OH group (here O1) is useful for evaluation in this context. The C—H⋯O hydrogen-to-oxygen distances for the interaction with the alcohol range from 2.29 to 5.98 Å (when the –CH3–OH moiety is pointing directly towards the C–H or completely turned away, respectively; Moore et al., 1989; Basnak et al., 1996). The C—H⋯O hydrogen-to-oxygen distances for the interaction with the furane ring oxygen atom (here O3) range from 2.26 to 3.43 Å (Greco & Tor, 2007; Basnak et al., 1996) with the vast majority of orientations allowing at least weak hydrogen bonding between this oxygen and the C6–H hydrogen atom. No systematic dependency between these two groups of distances was found, i.e. a very short or long hydrogen bond with the ring oxygen atom does neither lead to particularly short nor long distances of the hydrogen atom to the methanoyl oxygen atom.
Only five of the related archived structures bear directly attached aromatic π-systems. In all five cases, the orientation of the sugar and the pyrimidine moieties are relatively similar in which the C6–H moiety points to some extent towards the methanoyl oxygen atom of the sugar, forming a weak intramolecular hydrogen bond and resulting in comparable molecular bends. The dihedral angles between the two aromatic systems do vary and range from 11.9° for a ferrocene substituent (Song et al., 2006) to 37.2° for a para-biphenyl substituent (Gayakhe et al., 2016), indicating that the extent of delocalization of the π-systems depends on the actual type of aromatic substituent but is not particularly strong in any case.
3. Supramolecular Features
In the crystal, molecules are linked by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds (Fig. 2 and Table 1). The molecules form rows propagating along the a-axis direction, which are connected to adjacent rows in the c-axis direction by classical hydrogen bonds and in the b-axis direction only by weaker C—H⋯O contacts between two sugar moieties (C4—H4A⋯O3i, two-directional). In the c- and (by bifurcation) a-axis directions, both classical and non-classical hydrogen bonds are present (O2–H2O⋯O5ii; O1—H1O⋯O2iv; N2—H2N⋯O1iii; C13—H13⋯O4; C14—H14⋯O4ii). These interactions lead to the formation of slabs lying parallel to the ac plane.
4. Synthesis and crystallization
The title compound was synthesized according to our recently reported method (Bhilare et al., 2016). This involves the cross-coupling reaction of 5-iodo-2′-deoxyuridine and 4-(dibenzofuranyl)boronic acid in the presence of Pd(OAc)2 and PTBS (phospha-triaza-adamantyl propane sulfonate) in water.
Synthesis of 5-(dibenzofuran-4-yl)-2′-deoxyuridine: To a solution of palladium acetate (1.12 mg, 1.0 mol %) and PTABS ligand (2.93 mg, 2.0 mol %) in degassed water (1.0 ml) at ambient temperature under N2 were added 5-iodo-2′-deoxyuridine (0.5 mmol) and the solution stirred for 5 min at 353 K. After that, the reaction mixture was allowed to cool to room temperature and then 4-(dibenzofuranyl)boronic acid (0.75 mmol) was added along with triethylamine (0.14 ml, 1.0 mmol) and degassed water (2.0 ml). The resulting solution was then stirred at 353 K for 3 h. The reaction progress was monitored by TLC. After the completion of reaction, the solvent was removed in vacuo and the resultant residue obtained was purified using in CH2Cl2:MeOH solvent system (96:4) to afford the desired product as a white solid (162 mg, 82% yield).
UV–visible absorption and fluorescence emission in methanol (10 µM) λabs = 286 nm λfl = 392,427. 1H NMR (400 MHz, DMSO-d6) δ 11.62 (s, 1H), 8.41 (s, 1H), 8.12 (d, J = 7.4 Hz, 1H), 8.06 (d, J = 7.7 Hz, 1H), 7.67 (t, J = 7.8 Hz, 2H), 7.49 (t, J = 7.7 Hz, 1H), 7.38 (t, J = 7.6 Hz, 2H), 6.28 (t, J = 6.7 Hz, 1H), 5.29 (d, J = 3.8 Hz, 1H), 4.87 (t, J = 4.9 Hz, 1H), 4.27 (s, 1H), 3.81 (d, J = 2.9 Hz, 1H), 3.54 (s, 2H), 2.29–2.14 (m, 2H). 13C NMR (101 MHz, DMSO-d6) δ 161.7, 155.3, 152.9, 150.0, 140.1, 128.3, 127.6, 123.8, 123.6, 123.2, 122.8, 121.1, 120.3, 117.8, 111.7, 108.8, 87.6, 84.5, 70.5, 61.4, 39.9. ESI–MS (m/z) = 395 (M+ + H+). Analysis calculated for C21H18N2O6: C, 63.96; H, 4.60; N, 7.10. Found: C, 63.85; H, 4.64; N, 6.98.
5. Refinement
Crystal data, data collection and structure . The two protons on oxygen (O1, O2) and the one on nitrogen (N2) were located and refined with a constraint for the atom—H distance (SHELXL instruction: SADI 0.05 O1 H1O O2 H2O N2 H2N), as otherwise the N—H distance became rather short and the O—H distances rather long. The respective orientations, i.e. the directions the hydrogen atoms are pointing to (particularly important for the alcohol functions), were refined without any restraints or constraints. The C-bound H atoms were included in calculated positions and treated as riding: C—H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 1574284
https://doi.org/10.1107/S2056989017013111/ds2247sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017013111/ds2247Isup2.hkl
Bond lengths in uracil bases with substitution at the C5 position. DOI: https://doi.org/10.1107/S2056989017013111/ds2247sup3.pdf
Data collection: X-AREA (Stoe & Cie, 2010); cell
X-AREA (Stoe & Cie, 2010); data reduction: X-AREA (Stoe & Cie, 2010); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: CIFTAB (Sheldrick, 2008) and PLATON (Spek, 2009).C21H18N2O6 | Dx = 1.531 Mg m−3 |
Mr = 394.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 14682 reflections |
a = 6.2899 (13) Å | θ = 6.5–54.3° |
b = 15.167 (3) Å | µ = 0.11 mm−1 |
c = 17.938 (4) Å | T = 170 K |
V = 1711.2 (6) Å3 | Needle, colourless |
Z = 4 | 0.46 × 0.09 × 0.09 mm |
F(000) = 824 |
Stoe IPDS2T diffractometer | 3696 independent reflections |
Radiation source: fine-focus sealed tube | 2704 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.110 |
ω scans | θmax = 27.1°, θmin = 3.4° |
Absorption correction: numerical face indexed (X-Red32 and X-Shape; Stoe & Cie, 2010) | h = −7→8 |
Tmin = 0.388, Tmax = 0.875 | k = −19→19 |
14640 measured reflections | l = −22→22 |
Refinement on F2 | 3 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.143 | w = 1/[σ2(Fo2) + (0.0841P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
3696 reflections | Δρmax = 0.34 e Å−3 |
274 parameters | Δρmin = −0.37 e Å−3 |
Experimental. The reaction was carried out in a Schlenk tube using Schlenk techniques under a nitrogen atmosphere. All other reagents and solvents were purchased commercially and used without any further purification. A UV–visible spectrum of the title compound (10 µM) was measured in methanol using a UV–visible spectrophotometer with a cell of 1 cm path length. A fluorescence spectrum of the same solution was obtained using a fluorescence spectrophotometer at 298 K using a 1 cm path-length cell. The reaction was monitored by thin layer chromatography using TLC silica gel 60 F254 precoated plates (Merck). Visualization was accomplished by irradiation with UV light. C, H, and N analyses was carried out locally. NMR data (1H, 13C) of the synthesized compound were recorded locally on 500 MHz spectrometers. Mass spectroscopic analysis was carried out with a mass spectrometer from Varian Inc, US: 10 Prostar Binary LC with 500 MS IT PDA detectors. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.4367 (6) | 0.5659 (2) | 0.66750 (19) | 0.0316 (8) | |
O2 | −0.1365 (5) | 0.6212 (3) | 0.62349 (19) | 0.0355 (8) | |
O3 | 0.3555 (5) | 0.6634 (2) | 0.52801 (16) | 0.0251 (7) | |
O4 | 0.0678 (6) | 0.6179 (2) | 0.33056 (18) | 0.0342 (8) | |
O5 | 0.5541 (6) | 0.4112 (2) | 0.26958 (17) | 0.0319 (8) | |
O6 | 0.6845 (5) | 0.4177 (2) | 0.54844 (17) | 0.0271 (7) | |
N1 | 0.3167 (6) | 0.5825 (2) | 0.4169 (2) | 0.0244 (8) | |
N2 | 0.3171 (7) | 0.5149 (3) | 0.3022 (2) | 0.0278 (8) | |
C1 | 0.3630 (8) | 0.6543 (3) | 0.6624 (2) | 0.0268 (10) | |
H1A | 0.4869 | 0.6946 | 0.6612 | 0.032* | |
H1B | 0.2787 | 0.6685 | 0.7074 | 0.032* | |
C2 | 0.2282 (7) | 0.6702 (3) | 0.5941 (2) | 0.0238 (9) | |
H2 | 0.1672 | 0.7310 | 0.5970 | 0.029* | |
C3 | 0.0472 (7) | 0.6046 (3) | 0.5800 (2) | 0.0256 (9) | |
H3 | 0.0978 | 0.5428 | 0.5880 | 0.031* | |
C4 | 0.0039 (7) | 0.6206 (3) | 0.4983 (3) | 0.0264 (9) | |
H4A | −0.1046 | 0.6672 | 0.4915 | 0.032* | |
H4B | −0.0458 | 0.5660 | 0.4735 | 0.032* | |
C5 | 0.2197 (7) | 0.6500 (3) | 0.4670 (2) | 0.0253 (9) | |
H5 | 0.2020 | 0.7067 | 0.4391 | 0.030* | |
C6 | 0.4901 (7) | 0.5330 (3) | 0.4377 (2) | 0.0233 (9) | |
H6 | 0.5481 | 0.5409 | 0.4862 | 0.028* | |
C7 | 0.5806 (7) | 0.4735 (3) | 0.3914 (2) | 0.0239 (9) | |
C8 | 0.4944 (7) | 0.4627 (3) | 0.3171 (3) | 0.0262 (9) | |
C9 | 0.2231 (8) | 0.5755 (3) | 0.3485 (2) | 0.0282 (10) | |
C10 | 0.7714 (7) | 0.4220 (3) | 0.4143 (2) | 0.0250 (9) | |
C11 | 0.8132 (7) | 0.4001 (3) | 0.4874 (2) | 0.0256 (10) | |
C12 | 0.7864 (8) | 0.3833 (3) | 0.6103 (2) | 0.0271 (10) | |
C13 | 0.7096 (8) | 0.3830 (3) | 0.6814 (3) | 0.0296 (10) | |
H13 | 0.5767 | 0.4090 | 0.6935 | 0.036* | |
C14 | 0.8351 (8) | 0.3429 (3) | 0.7351 (3) | 0.0321 (10) | |
H14 | 0.7868 | 0.3412 | 0.7853 | 0.039* | |
C15 | 1.0316 (8) | 0.3047 (3) | 0.7172 (3) | 0.0310 (10) | |
H15 | 1.1139 | 0.2775 | 0.7552 | 0.037* | |
C16 | 1.1061 (8) | 0.3060 (3) | 0.6454 (3) | 0.0306 (10) | |
H16 | 1.2393 | 0.2802 | 0.6334 | 0.037* | |
C17 | 0.9829 (7) | 0.3460 (3) | 0.5904 (3) | 0.0262 (9) | |
C18 | 0.9993 (7) | 0.3562 (3) | 0.5105 (3) | 0.0250 (9) | |
C19 | 1.1478 (7) | 0.3293 (3) | 0.4577 (3) | 0.0280 (10) | |
H19 | 1.2741 | 0.2993 | 0.4720 | 0.034* | |
C20 | 1.1057 (7) | 0.3474 (3) | 0.3848 (3) | 0.0294 (10) | |
H20 | 1.2028 | 0.3278 | 0.3477 | 0.035* | |
C21 | 0.9242 (8) | 0.3939 (3) | 0.3626 (3) | 0.0281 (10) | |
H21 | 0.9041 | 0.4067 | 0.3112 | 0.034* | |
H2O | −0.097 (9) | 0.608 (4) | 0.676 (3) | 0.037 (15)* | |
H2N | 0.266 (9) | 0.506 (4) | 0.255 (3) | 0.034 (14)* | |
H1O | 0.567 (10) | 0.562 (5) | 0.644 (4) | 0.07 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0278 (19) | 0.0285 (17) | 0.0385 (19) | 0.0033 (13) | −0.0009 (14) | 0.0040 (14) |
O2 | 0.0208 (17) | 0.054 (2) | 0.0320 (19) | 0.0045 (15) | 0.0025 (13) | 0.0041 (16) |
O3 | 0.0267 (17) | 0.0264 (15) | 0.0223 (16) | −0.0019 (12) | 0.0004 (12) | −0.0025 (12) |
O4 | 0.0333 (19) | 0.0388 (18) | 0.0305 (17) | 0.0095 (15) | −0.0064 (14) | −0.0014 (15) |
O5 | 0.0370 (19) | 0.0331 (17) | 0.0255 (16) | 0.0016 (14) | 0.0004 (14) | −0.0086 (14) |
O6 | 0.0269 (17) | 0.0286 (16) | 0.0259 (15) | 0.0040 (13) | 0.0028 (13) | 0.0018 (12) |
N1 | 0.024 (2) | 0.0249 (18) | 0.0243 (18) | 0.0037 (15) | −0.0004 (15) | 0.0000 (15) |
N2 | 0.033 (2) | 0.0299 (19) | 0.0205 (19) | 0.0018 (16) | −0.0034 (16) | −0.0039 (15) |
C1 | 0.029 (2) | 0.024 (2) | 0.028 (2) | −0.0031 (18) | 0.0007 (18) | −0.0005 (18) |
C2 | 0.025 (2) | 0.021 (2) | 0.025 (2) | 0.0013 (16) | 0.0016 (18) | 0.0007 (17) |
C3 | 0.022 (2) | 0.023 (2) | 0.031 (2) | 0.0002 (17) | 0.0024 (17) | 0.0028 (18) |
C4 | 0.022 (2) | 0.026 (2) | 0.031 (2) | 0.0039 (17) | −0.0022 (19) | −0.0032 (18) |
C5 | 0.032 (2) | 0.021 (2) | 0.023 (2) | 0.0024 (17) | −0.0011 (18) | −0.0010 (17) |
C6 | 0.024 (2) | 0.023 (2) | 0.023 (2) | −0.0023 (16) | −0.0033 (16) | −0.0002 (16) |
C7 | 0.024 (2) | 0.021 (2) | 0.026 (2) | −0.0018 (16) | 0.0020 (17) | 0.0012 (17) |
C8 | 0.027 (2) | 0.024 (2) | 0.027 (2) | −0.0021 (17) | 0.0014 (18) | 0.0015 (17) |
C9 | 0.032 (3) | 0.030 (2) | 0.023 (2) | −0.002 (2) | −0.0005 (18) | −0.0014 (18) |
C10 | 0.026 (2) | 0.020 (2) | 0.029 (2) | −0.0015 (17) | 0.0010 (18) | −0.0024 (18) |
C11 | 0.027 (3) | 0.020 (2) | 0.029 (2) | 0.0003 (17) | 0.0060 (18) | −0.0031 (16) |
C12 | 0.029 (2) | 0.023 (2) | 0.030 (2) | 0.0016 (18) | −0.0041 (19) | 0.0003 (18) |
C13 | 0.036 (3) | 0.023 (2) | 0.030 (2) | 0.0030 (19) | 0.001 (2) | 0.0011 (18) |
C14 | 0.040 (3) | 0.027 (2) | 0.029 (2) | −0.004 (2) | −0.003 (2) | −0.0001 (19) |
C15 | 0.030 (3) | 0.028 (2) | 0.036 (3) | 0.0010 (19) | −0.009 (2) | 0.0030 (19) |
C16 | 0.030 (3) | 0.022 (2) | 0.040 (3) | 0.0015 (17) | −0.006 (2) | −0.004 (2) |
C17 | 0.024 (2) | 0.023 (2) | 0.032 (2) | −0.0019 (17) | −0.0003 (19) | −0.0024 (18) |
C18 | 0.025 (2) | 0.019 (2) | 0.031 (2) | −0.0012 (17) | 0.0012 (18) | 0.0005 (17) |
C19 | 0.026 (2) | 0.017 (2) | 0.041 (3) | 0.0010 (16) | 0.004 (2) | −0.0001 (18) |
C20 | 0.027 (2) | 0.029 (2) | 0.033 (3) | 0.0008 (18) | 0.0083 (19) | −0.0053 (19) |
C21 | 0.033 (3) | 0.025 (2) | 0.026 (2) | −0.0032 (18) | 0.0028 (19) | −0.0045 (18) |
O1—C1 | 1.423 (6) | C5—H5 | 1.0000 |
O1—H1O | 0.92 (6) | C6—C7 | 1.353 (6) |
O2—C3 | 1.417 (6) | C6—H6 | 0.9500 |
O2—H2O | 1.00 (5) | C7—C8 | 1.447 (6) |
O3—C5 | 1.403 (5) | C7—C10 | 1.489 (6) |
O3—C2 | 1.435 (5) | C10—C11 | 1.379 (6) |
O4—C9 | 1.213 (6) | C10—C21 | 1.402 (6) |
O5—C8 | 1.216 (5) | C11—C18 | 1.408 (6) |
O6—C12 | 1.384 (5) | C12—C13 | 1.364 (7) |
O6—C11 | 1.387 (5) | C12—C17 | 1.405 (6) |
N1—C9 | 1.366 (6) | C13—C14 | 1.386 (7) |
N1—C6 | 1.375 (6) | C13—H13 | 0.9500 |
N1—C5 | 1.492 (5) | C14—C15 | 1.403 (7) |
N2—C9 | 1.373 (6) | C14—H14 | 0.9500 |
N2—C8 | 1.393 (6) | C15—C16 | 1.370 (7) |
N2—H2N | 0.91 (5) | C15—H15 | 0.9500 |
C1—C2 | 1.508 (6) | C16—C17 | 1.394 (6) |
C1—H1A | 0.9900 | C16—H16 | 0.9500 |
C1—H1B | 0.9900 | C17—C18 | 1.445 (6) |
C2—C3 | 1.533 (6) | C18—C19 | 1.391 (6) |
C2—H2 | 1.0000 | C19—C20 | 1.364 (7) |
C3—C4 | 1.511 (6) | C19—H19 | 0.9500 |
C3—H3 | 1.0000 | C20—C21 | 1.399 (7) |
C4—C5 | 1.535 (7) | C20—H20 | 0.9500 |
C4—H4A | 0.9900 | C21—H21 | 0.9500 |
C4—H4B | 0.9900 | ||
C1—O1—H1O | 109 (5) | C6—C7—C10 | 121.3 (4) |
C3—O2—H2O | 106 (3) | C8—C7—C10 | 119.8 (4) |
C5—O3—C2 | 108.4 (3) | O5—C8—N2 | 118.5 (4) |
C12—O6—C11 | 106.8 (3) | O5—C8—C7 | 127.0 (4) |
C9—N1—C6 | 122.9 (4) | N2—C8—C7 | 114.4 (4) |
C9—N1—C5 | 114.7 (4) | O4—C9—N1 | 122.9 (4) |
C6—N1—C5 | 122.4 (4) | O4—C9—N2 | 122.8 (4) |
C9—N2—C8 | 127.5 (4) | N1—C9—N2 | 114.2 (4) |
C9—N2—H2N | 121 (4) | C11—C10—C21 | 115.1 (4) |
C8—N2—H2N | 112 (4) | C11—C10—C7 | 122.8 (4) |
O1—C1—C2 | 112.7 (4) | C21—C10—C7 | 122.0 (4) |
O1—C1—H1A | 109.1 | C10—C11—O6 | 126.3 (4) |
C2—C1—H1A | 109.1 | C10—C11—C18 | 123.5 (4) |
O1—C1—H1B | 109.1 | O6—C11—C18 | 110.2 (4) |
C2—C1—H1B | 109.1 | C13—C12—O6 | 125.9 (4) |
H1A—C1—H1B | 107.8 | C13—C12—C17 | 123.2 (4) |
O3—C2—C1 | 110.2 (4) | O6—C12—C17 | 110.8 (4) |
O3—C2—C3 | 103.3 (3) | C12—C13—C14 | 116.8 (5) |
C1—C2—C3 | 116.7 (4) | C12—C13—H13 | 121.6 |
O3—C2—H2 | 108.8 | C14—C13—H13 | 121.6 |
C1—C2—H2 | 108.8 | C13—C14—C15 | 121.5 (5) |
C3—C2—H2 | 108.8 | C13—C14—H14 | 119.2 |
O2—C3—C4 | 111.0 (4) | C15—C14—H14 | 119.2 |
O2—C3—C2 | 113.5 (4) | C16—C15—C14 | 120.8 (5) |
C4—C3—C2 | 101.0 (4) | C16—C15—H15 | 119.6 |
O2—C3—H3 | 110.4 | C14—C15—H15 | 119.6 |
C4—C3—H3 | 110.4 | C15—C16—C17 | 118.8 (5) |
C2—C3—H3 | 110.4 | C15—C16—H16 | 120.6 |
C3—C4—C5 | 104.0 (4) | C17—C16—H16 | 120.6 |
C3—C4—H4A | 111.0 | C16—C17—C12 | 118.9 (4) |
C5—C4—H4A | 111.0 | C16—C17—C18 | 135.2 (4) |
C3—C4—H4B | 111.0 | C12—C17—C18 | 105.8 (4) |
C5—C4—H4B | 111.0 | C19—C18—C11 | 119.8 (4) |
H4A—C4—H4B | 109.0 | C19—C18—C17 | 133.7 (4) |
O3—C5—N1 | 108.6 (3) | C11—C18—C17 | 106.4 (4) |
O3—C5—C4 | 107.2 (3) | C20—C19—C18 | 117.6 (4) |
N1—C5—C4 | 112.5 (4) | C20—C19—H19 | 121.2 |
O3—C5—H5 | 109.5 | C18—C19—H19 | 121.2 |
N1—C5—H5 | 109.5 | C19—C20—C21 | 122.2 (4) |
C4—C5—H5 | 109.5 | C19—C20—H20 | 118.9 |
C7—C6—N1 | 122.1 (4) | C21—C20—H20 | 118.9 |
C7—C6—H6 | 118.9 | C20—C21—C10 | 121.7 (4) |
N1—C6—H6 | 118.9 | C20—C21—H21 | 119.2 |
C6—C7—C8 | 118.8 (4) | C10—C21—H21 | 119.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3i | 0.99 | 2.61 | 3.439 (6) | 142 |
C6—H6···O6 | 0.95 | 2.34 | 2.915 (5) | 119 |
C13—H13···O1 | 0.95 | 2.58 | 3.271 (6) | 130 |
C21—H21···O5 | 0.95 | 2.33 | 2.876 (6) | 116 |
C13—H13···O4ii | 0.95 | 2.65 | 3.194 (6) | 117 |
C14—H14···O4ii | 0.95 | 2.45 | 3.115 (6) | 127 |
C1—H1B···O5ii | 0.99 | 2.66 | 3.401 (6) | 132 |
O2—H2O···O5ii | 1.00 (5) | 1.72 (5) | 2.716 (5) | 174 (5) |
N2—H2N···O1iii | 0.91 (5) | 2.30 (5) | 3.144 (5) | 154 (5) |
O1—H1O···O2iv | 0.92 (6) | 2.10 (6) | 2.922 (5) | 148 (6) |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+1/2, −y+1, z+1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) x+1, y, z. |
Acknowledgements
ARK and CS acknowledge 'The Alexander von Humboldt Foundation' for the research cooperation programme, which is also thanked for the equipment grant to ARK. We also thank the University Grants Commission India for a UGC–SAP fellowship for VG. YB and CS gratefully acknowledges funding from the ERC.
Funding information
Funding for this research was provided by: Alexander von Humboldt-Stiftung (grant No. 3.4 - IP - DEU/1131213 to A. R. Kapdi, C. Schulzke); University Grants Commission (scholarship to V. Gayakhe); FP7 Ideas: European Research Council (grant No. 281257 to C. Schulzke).
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