1. Chemical context
Representatives of the class of 1,3,5-trisubstituted 2,4,6-trialkylbenzenes have been shown to have the ability to act as artificial carbohydrate receptors. Depending on the nature of their building blocks, these compounds display different, interesting binding efficiencies and selectivities towards carbohydrates (Mazik, 2009, 2012; Stapf et al., 2020). Our systematic studies have shown the enormous potential of this acyclic receptor architecture for versatile structural modifications, which enable the identification of interesting structure–activity relationships. For example, we have observed that the combination of two 2-aminopyridine units with another recognition group provides receptors having a binding preference for β-glucoside vs β-galactoside (Mazik & Kuschel, 2008; Mazik & Geffert, 2011; Stapf et al., 2020).
{1-[(3,5-Bis{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzyl)amino]cyclopentyl}methanol, 1, represents a triethylbenzene derivative bearing, in addition to the above-mentioned pyridinyl units, a 1-hydroxymethyl-cyclopentylamino group. The crystal structures of the monohydrate, 1a, and the methanol solvate, 1b, are described here.
2. Structural commentary
Compounds 1a and 1b crystallize in the space groups P21/c and P, respectively. The molecular structures depicted in Figs. 1 and 2 reveal similar host geometries with a fully alternating arrangement of the substituents above and below the plane of the central arene ring [ab'ab'ab' pattern, a = above, b = below (a′/b′ = Et above/below); for a discussion on the conformations of triethylbenzene-based compounds, see: Koch et al., 2017; Schulze et al., 2017]. In other words, the three functionalized side arms point to one face of the central benzene ring and participate in the formation of hydrogen bonds with the guest solvent molecule, while the ethyl groups are directed to the opposite side. The heterocyclic units are inclined by 62.4 (1) and 73.0 (1)° for 1a [78.9 (1) and 85.1 (1)° for 1b] with respect to the benzene ring. The cyclopentane rings adopt a slightly distorted envelope conformation with C33 (1a) and C31 (1b) as the flap.
| Figure 1 Perspective views of the structures of the 1:1 host–guest complexes, 1a (a) and 1b (b), including atom labelling. Anisotropic displacement ellipsoids are drawn at the 50% probability level. |
| Figure 2 Ball-and-stick representations (side views) of the 1:1 host–guest complexes, 1a (a) and 1b (b). |
3. Supramolecular features
The crystal structures of 1a and 1b are composed of inversion-symmetric dimers of 1:1 host–guest complexes (Fig. 3). The donor/acceptor properties of the solvent species have, however, a marked influence on the patterns of hydrogen-bonding interactions. In the crystal of 1a, the dimeric structural unit is held together by classical hydrogen bonds (N5—H5⋯O1Wi and O1W—H2W⋯N5; symmetry code as given in Table 1) that contribute to the formation of a cyclic supramolecular synthon with a graph-set motif R44(8). Within this dimeric unit, the oxygen atom of the water molecules acts as a trifurcated acceptor, as it is involved in the formation of an O—H⋯O bond [d(H⋯O) = 1.83 (1) Å] and two Namine—H⋯O interactions [d(H⋯O) = 2.50 (1) and 2.52 (1) Å]. The H atoms of the water molecule participate in an asymmetric fashion in O—H⋯N bonding [d(H⋯N) = 2.03 (1) and 1.93 (1) Å] with pyridine atom N2 and amine atom N5, respectively, of different host molecules. The interactions between the host molecules are confined to only one N—H⋯O hydrogen bond [d(H⋯O) = 2.05 (1) Å] per molecule. In the crystal of 1a, the complexes are connected via C—H⋯π interactions [d(H⋯Cg) = 2.69 and 2.84 Å], forming a three-dimensional network. An portion of the crystal structure is displayed in Fig. 4. The presence of the alcohol solvent in 1b reduces the number of hydrogen bonds within the dimeric structural unit (Table 2). In this case, the complex components create a continuous pattern of hydrogen bonds in the structure: N—H⋯Osolv—H⋯N—H⋯Ohost—H⋯Npyr [d(H⋯O) = 2.01 (3) and 2.36 (3) Å; d(H⋯N) = 1.90 and 1.97 Å]. While one of the amine hydrogen atoms is excluded from hydrogen bonding, a second one contributes by the formation of an intramolecular N—H⋯O bond. Cross-linking of the complexes via C—H⋯π and π–π interactions [Cg2⋯Cg2iv = 4.076 (2) Å; Cg2 is the centroid of the C14–C18/N2 ring; symmetry code: (iv) −x + 2, −y + 1, −z + 1] results in a three-dimensional supramolecular architecture. A view of the crystal structure along the b axis reveals channel-like lattice voids in which the disordered solvent molecules are accommodated (Fig. 5).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | O1W—H2W⋯N5 | 0.87 (1) | 1.93 (1) | 2.8018 (14) | 175 (2) | O1W—H1W⋯N2i | 0.86 (1) | 2.03 (1) | 2.8780 (15) | 166 (2) | O1—H1A⋯O1Wi | 0.87 (1) | 1.83 (1) | 2.6993 (14) | 176 (2) | N5—H5⋯O1Wi | 0.90 (1) | 2.52 (1) | 3.3302 (14) | 151 (1) | N3—H3⋯O1i | 0.89 (1) | 2.05 (1) | 2.9115 (15) | 162 (2) | N1—H1⋯O1Wi | 0.89 (1) | 2.50 (1) | 3.2618 (16) | 145 (1) | C32—H32B⋯Cg1ii | 0.99 | 2.69 | 3.666 (2) | 169 | C25—H25⋯Cg2iii | 0.95 | 2.84 | 3.728 (2) | 156 | Symmetry codes: (i) ; (ii) ; (iii) x+1, y, z. | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯O1A | 0.94 (3) | 2.01 (3) | 2.930 (3) | 162 (2) | C15—H15⋯O1A | 0.95 | 2.56 | 3.318 (3) | 137 | N5—H5⋯O1 | 0.90 (3) | 2.36 (3) | 2.823 (3) | 112 (2) | O1—H1A⋯N4i | 0.84 | 1.90 | 2.741 (3) | 174 | O1A—H1AA⋯N5i | 0.84 | 1.97 | 2.798 (3) | 170 | C27—H27A⋯Cg1ii | 0.98 | 2.67 | 3.541 (3) | 148 | C32—H32B⋯Cg3iii | 0.98 | 2.69 | 3.614 (3) | 156 | Symmetry codes: (i) ; (ii) ; (iii) x+1, y, z. | |
| Figure 3 Supramolecular motifs in the crystal structures of 1a (a) and 1b (b). For the sake of clarity, H atoms of the host molecules not involved in hydrogen bonding are omitted. |
| Figure 4 Packing diagram of 1a. Dashed lines represent hydrogen bonds. H atoms not involved in the hydrogen bonds are omitted. |
| Figure 5 Packing diagram of 1b viewed down the b axis. Dashed lines represent hydrogen bonds, dashed double lines π–π interactions. Areas occupied by disordered solvent molecules are highlighted as grey ellipsoids. H atoms of the host molecules not involved in the hydrogen bonds are omitted. |
4. Database survey
A search in the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016) for 1,3,5-trisubstituted 2,4,6-trialkylbenzene derivatives containing the 4,6-dimethylpyridin-2-yl-aminomethyl subunit resulted in five hits. They include 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-trimethylbenzene (refcode QAPVAF; Mazik et al., 2005), which has proven to be an effective receptor for complex formation with methyl β-D-glucopyranoside in the solid state, as well as the ethanol solvates of 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-trimethylbenzene (RAJYUX; Mazik et al., 2004) and of 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene (RAJZAE; Mazik et al., 2004). In the crystals of the ethanol solvates (Mazik et al., 2004), the functionalized side arms of the corresponding host are arranged in an aab fashion with respect to the benzene plane. In addition to the solvates of the symmetrical trisubstituted trimethyl- and triethylbenzene derivatives, the crystal structures of the solvates of two triethylbenzene-based compounds containing one or two phenanthrolinyl groups (ROKJEH, ROKJEH01; Mazik & Hartmann, 2008; Mazik et al., 2009) in addition to the 2-aminopyridine unit(s) have also been reported. In the case of 1-[N-(1,10-phenanthrolin-2-yl-carbonyl)aminomethyl]-3,5-bis[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene, three water molecules are located in the binding pocket created by the heterocyclic units of the host (Mazik & Hartmann, 2008), whereas the binding pocket of 1,3-bis[N-(1,10-phenanthrolin-2-yl-carbonyl)aminomethyl]-5-[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene is filled with one ethanol and two water molecules (Mazik et al., 2009). The above-mentioned aggregates are stabilized by eight and ten hydrogen bonds, respectively.
5. Synthesis and crystallization
To a solution of 1-amino-1-cyclopentylmethanol (1.48 mmol) in acetonitrile (20 ml) was added 1-bromomethyl-3,5-bis[(4,6-dimethylpyridin-2-yl)aminomethyl-2,4,6-triethylbenzene (0.71 mmol) dissolved in tetrahydrofuran/acetonitrile (20 ml, 1:1 v/v). The reaction mixture was stirred at room temperature and under exclusion of light. The completion of the reaction was monitored by TLC. After evaporation of the solvents in vacuo and purification of the yellowish crude product via column chromatography (SiO2; chloroform/methanol 7:1 v/v), compound 1 was obtained as a white solid. Yield: 33%; Rf = 0.26 (chloroform/methanol 7:1 v/v); m.p. 375 K. Crystals of 1a and 1b suitable for single crystal X-ray diffraction were grown by slow evaporation of the respective solvent (acetonitrile in case of 1a) at ambient temperature. 1H NMR (500 MHz, CDCl3, ppm) δ = 1.23 (t+t, 9H, J = 7.3 Hz), 1.55–1.65 (m, 4H), 1.68–1.77 (m, 4H), 2.23 (s, 6H), 2.36 (s, 6H), 2.70 (q, 2H, J = 7.3 Hz), 2.82 (br, 4H), 3.46 (s, 2H), 3.74 (br, 2H), 4.36 (br, 4H), 6.13 (s, 2H), 6.33 (s, 2H). 13C NMR (125 MHz, CDCl3, ppm) δ = 16.7, 16.9, 21.1, 22.9, 23.4, 23.9, 24.2, 33.5, 40.5 (2C), 64.7, 67.7, 103.8, 113.6, 132.8 (2C), 143.8 (2C), 148.8, 156.2, 158.2.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3. N- and O-bound H atoms in 1a were located in a difference-Fourier map and refined freely with distance restraints of N—H = 0.89 (1) Å and O—H = 0.85 (1) Å. For 1b, N-bound H atoms were refined freely, while O-bound H atoms were treated as riding with O—H = 0.84 Å. All other H atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.99 Å, and with Uiso(H) = 1.5Ueq(C) for methyl groups and Uiso(H) = 1.2Ueq(C) for other H atoms. The crystal structure 1b contains highly disordered solvent molecules that could not be refined to an acceptable level. Thus, the SQUEEZE routine (Spek, 2015) in the PLATON (Spek, 2020) program was used to generate a modified data set in which the contribution of the disordered molecules to the structure amplitudes is eliminated. These solvent molecules are not considered in the given chemical formula. The void volume of 267.9 Å3 occupied by the disordered solvent represents 14.3% of the cell volume, and the calculated electron count was 65 per void.
| 1b | 1b | Crystal data | Chemical formula | C35H51N5O·H2O | C35H51N5O·CH4O | Mr | 575.82 | 589.85 | Crystal system, space group | Monoclinic, P21/c | Triclinic, P | Temperature (K) | 100 | 100 | a, b, c (Å) | 13.2239 (7), 15.3576 (8), 17.1061 (8) | 12.1169 (4), 13.2380 (5), 13.6258 (5) | α, β, γ (°) | 90, 107.0289 (17), 90 | 68.373 (2), 79.379 (2), 67.392 (2) | V (Å3) | 3321.7 (3) | 1873.32 (12) | Z | 4 | 2 | Radiation type | Mo Kα | Mo Kα | μ (mm−1) | 0.07 | 0.07 | Crystal size (mm) | 0.45 × 0.32 × 0.10 | 0.56 × 0.34 × 0.32 | | Data collection | Diffractometer | Bruker X8 APEXII CCD | Bruker X8 APEXII CCD | No. of measured, independent and observed [I > 2σ(I)] reflections | 28794, 7467, 5791 | 32191, 7654, 5160 | Rint | 0.034 | 0.022 | (sin θ/λ)max (Å−1) | 0.647 | 0.626 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.114, 1.03 | 0.065, 0.184, 1.21 | No. of reflections | 7467 | 7654 | No. of parameters | 410 | 410 | No. of restraints | 6 | 0 | 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 | Δρmax, Δρmin (e Å−3) | 0.27, −0.20 | 0.64, −0.39 | Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and ORTEP-3 for Windows (Farrugia, 2012). | |
Supporting information
For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
{1-[(3,5-Bis{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzyl)amino]cyclopentyl}methanol monohydrate (1a)
top Crystal data top C35H51N5O·H2O | F(000) = 1256 |
Mr = 575.82 | Dx = 1.151 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.2239 (7) Å | Cell parameters from 9674 reflections |
b = 15.3576 (8) Å | θ = 2.2–28.2° |
c = 17.1061 (8) Å | µ = 0.07 mm−1 |
β = 107.0289 (17)° | T = 100 K |
V = 3321.7 (3) Å3 | Irregular, colourless |
Z = 4 | 0.45 × 0.32 × 0.10 mm |
Data collection top Bruker X8 APEXII CCD diffractometer | Rint = 0.034 |
phi and ω scans | θmax = 27.4°, θmin = 2.1° |
28794 measured reflections | h = −17→17 |
7467 independent reflections | k = −19→17 |
5791 reflections with I > 2σ(I) | l = −22→21 |
Refinement top Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.8757P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
7467 reflections | Δρmax = 0.27 e Å−3 |
410 parameters | Δρmin = −0.20 e Å−3 |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.21807 (7) | 0.54810 (6) | 0.00959 (6) | 0.0238 (2) | |
N1 | −0.11044 (9) | 0.24557 (8) | −0.12255 (7) | 0.0218 (2) | |
H1 | −0.0834 (13) | 0.2969 (7) | −0.1039 (10) | 0.036 (5)* | |
N2 | −0.23912 (9) | 0.33295 (7) | −0.20586 (6) | 0.0198 (2) | |
N3 | 0.33881 (9) | 0.29584 (8) | 0.05481 (7) | 0.0223 (3) | |
H3 | 0.3046 (12) | 0.3464 (7) | 0.0466 (10) | 0.036 (5)* | |
N4 | 0.44662 (8) | 0.20100 (7) | 0.00817 (7) | 0.0201 (2) | |
N5 | −0.03784 (8) | 0.45806 (7) | 0.12196 (6) | 0.0176 (2) | |
H5 | −0.0752 (11) | 0.4402 (10) | 0.0720 (6) | 0.024 (4)* | |
C1 | −0.03521 (10) | 0.26699 (8) | 0.06516 (7) | 0.0163 (3) | |
C2 | −0.00019 (10) | 0.21235 (8) | 0.01228 (7) | 0.0161 (3) | |
C3 | 0.10826 (10) | 0.20103 (8) | 0.02240 (7) | 0.0167 (3) | |
C4 | 0.18206 (10) | 0.24315 (8) | 0.08766 (7) | 0.0169 (3) | |
C5 | 0.14833 (10) | 0.30214 (8) | 0.13754 (7) | 0.0172 (3) | |
C6 | 0.03906 (10) | 0.31377 (8) | 0.12622 (7) | 0.0166 (3) | |
C7 | −0.15304 (10) | 0.27362 (9) | 0.05636 (8) | 0.0197 (3) | |
H7A | −0.1936 | 0.2693 | −0.0022 | 0.024* | |
H7B | −0.1682 | 0.3311 | 0.0766 | 0.024* | |
C8 | −0.18900 (11) | 0.20182 (10) | 0.10409 (9) | 0.0264 (3) | |
H8A | −0.1753 | 0.1448 | 0.0835 | 0.040* | |
H8B | −0.2649 | 0.2080 | 0.0971 | 0.040* | |
H8C | −0.1499 | 0.2066 | 0.1622 | 0.040* | |
C9 | 0.14599 (11) | 0.14569 (9) | −0.03707 (8) | 0.0223 (3) | |
H9A | 0.2149 | 0.1684 | −0.0399 | 0.027* | |
H9B | 0.0949 | 0.1512 | −0.0922 | 0.027* | |
C10 | 0.15839 (13) | 0.04917 (10) | −0.01346 (10) | 0.0335 (4) | |
H10A | 0.2087 | 0.0431 | 0.0412 | 0.050* | |
H10B | 0.1847 | 0.0173 | −0.0532 | 0.050* | |
H10C | 0.0897 | 0.0254 | −0.0133 | 0.050* | |
C11 | 0.22863 (10) | 0.35482 (9) | 0.20189 (8) | 0.0215 (3) | |
H11A | 0.1992 | 0.4135 | 0.2052 | 0.026* | |
H11B | 0.2932 | 0.3620 | 0.1845 | 0.026* | |
C12 | 0.25915 (12) | 0.31327 (10) | 0.28712 (8) | 0.0288 (3) | |
H12A | 0.1950 | 0.3008 | 0.3028 | 0.043* | |
H12B | 0.3042 | 0.3535 | 0.3268 | 0.043* | |
H12C | 0.2977 | 0.2590 | 0.2863 | 0.043* | |
C13 | −0.08201 (10) | 0.17532 (9) | −0.06179 (8) | 0.0190 (3) | |
H13A | −0.0524 | 0.1251 | −0.0840 | 0.023* | |
H13B | −0.1451 | 0.1556 | −0.0468 | 0.023* | |
C14 | −0.21009 (10) | 0.25244 (9) | −0.17714 (7) | 0.0181 (3) | |
C15 | −0.27565 (10) | 0.17971 (9) | −0.20134 (8) | 0.0206 (3) | |
H15 | −0.2528 | 0.1238 | −0.1796 | 0.025* | |
C16 | −0.37413 (11) | 0.19050 (9) | −0.25737 (9) | 0.0246 (3) | |
C17 | −0.40303 (11) | 0.27384 (9) | −0.28877 (8) | 0.0237 (3) | |
H17 | −0.4696 | 0.2832 | −0.3282 | 0.028* | |
C18 | −0.33386 (10) | 0.34256 (9) | −0.26202 (8) | 0.0205 (3) | |
C19 | −0.44869 (13) | 0.11508 (11) | −0.28255 (12) | 0.0432 (4) | |
H19A | −0.4083 | 0.0607 | −0.2750 | 0.065* | |
H19B | −0.4893 | 0.1213 | −0.3402 | 0.065* | |
H19C | −0.4972 | 0.1140 | −0.2489 | 0.065* | |
C20 | −0.36075 (12) | 0.43342 (10) | −0.29491 (9) | 0.0282 (3) | |
H20A | −0.3585 | 0.4732 | −0.2497 | 0.042* | |
H20B | −0.4319 | 0.4338 | −0.3338 | 0.042* | |
H20C | −0.3094 | 0.4523 | −0.3227 | 0.042* | |
C21 | 0.29964 (10) | 0.22967 (9) | 0.09957 (8) | 0.0201 (3) | |
H21A | 0.3387 | 0.2332 | 0.1585 | 0.024* | |
H21B | 0.3115 | 0.1711 | 0.0797 | 0.024* | |
C22 | 0.40895 (10) | 0.28164 (9) | 0.01095 (8) | 0.0191 (3) | |
C23 | 0.44048 (11) | 0.35362 (9) | −0.02740 (8) | 0.0227 (3) | |
H23 | 0.4112 | 0.4096 | −0.0245 | 0.027* | |
C24 | 0.51400 (11) | 0.34216 (9) | −0.06903 (9) | 0.0249 (3) | |
C25 | 0.55286 (11) | 0.25789 (9) | −0.07272 (9) | 0.0241 (3) | |
H25 | 0.6034 | 0.2474 | −0.1013 | 0.029* | |
C26 | 0.51739 (10) | 0.19036 (9) | −0.03474 (8) | 0.0217 (3) | |
C27 | 0.55221 (14) | 0.41751 (11) | −0.10917 (11) | 0.0386 (4) | |
H27A | 0.5240 | 0.4122 | −0.1687 | 0.058* | |
H27B | 0.6297 | 0.4171 | −0.0935 | 0.058* | |
H27C | 0.5278 | 0.4723 | −0.0914 | 0.058* | |
C28 | 0.55646 (13) | 0.09887 (10) | −0.03838 (10) | 0.0306 (3) | |
H28A | 0.5931 | 0.0787 | 0.0170 | 0.046* | |
H28B | 0.6054 | 0.0978 | −0.0717 | 0.046* | |
H28C | 0.4963 | 0.0605 | −0.0629 | 0.046* | |
C29 | −0.00203 (10) | 0.38089 (8) | 0.17448 (8) | 0.0190 (3) | |
H29A | −0.0616 | 0.3563 | 0.1914 | 0.023* | |
H29B | 0.0547 | 0.3976 | 0.2243 | 0.023* | |
C30 | −0.10008 (10) | 0.52576 (8) | 0.14971 (8) | 0.0192 (3) | |
C31 | −0.02821 (11) | 0.57698 (9) | 0.22365 (8) | 0.0239 (3) | |
H31A | 0.0443 | 0.5526 | 0.2400 | 0.029* | |
H31B | −0.0245 | 0.6391 | 0.2094 | 0.029* | |
C32 | −0.07871 (14) | 0.56730 (11) | 0.29311 (9) | 0.0360 (4) | |
H32A | −0.0488 | 0.5167 | 0.3281 | 0.043* | |
H32B | −0.0677 | 0.6204 | 0.3274 | 0.043* | |
C33 | −0.19561 (13) | 0.55366 (10) | 0.24928 (10) | 0.0341 (4) | |
H33A | −0.2308 | 0.6094 | 0.2284 | 0.041* | |
H33B | −0.2323 | 0.5265 | 0.2859 | 0.041* | |
C34 | −0.19394 (11) | 0.49275 (9) | 0.17924 (8) | 0.0230 (3) | |
H34A | −0.2613 | 0.4962 | 0.1346 | 0.028* | |
H34B | −0.1823 | 0.4317 | 0.1985 | 0.028* | |
C35 | −0.14183 (11) | 0.58756 (9) | 0.07718 (8) | 0.0218 (3) | |
H35A | −0.1743 | 0.6388 | 0.0954 | 0.026* | |
H35B | −0.0816 | 0.6084 | 0.0589 | 0.026* | |
O1W | 0.12410 (8) | 0.54814 (6) | 0.08143 (6) | 0.0228 (2) | |
H1A | −0.1888 (14) | 0.5189 (11) | −0.0219 (10) | 0.053 (6)* | |
H1W | 0.1623 (13) | 0.5760 (11) | 0.1234 (8) | 0.049 (6)* | |
H2W | 0.0765 (13) | 0.5196 (12) | 0.0970 (12) | 0.056 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0248 (5) | 0.0247 (5) | 0.0211 (5) | 0.0028 (4) | 0.0057 (4) | −0.0022 (4) |
N1 | 0.0216 (6) | 0.0227 (6) | 0.0174 (5) | −0.0049 (5) | 0.0001 (5) | 0.0022 (5) |
N2 | 0.0228 (6) | 0.0218 (6) | 0.0145 (5) | −0.0014 (4) | 0.0050 (4) | −0.0001 (5) |
N3 | 0.0219 (6) | 0.0215 (6) | 0.0262 (6) | 0.0011 (5) | 0.0114 (5) | 0.0022 (5) |
N4 | 0.0202 (5) | 0.0211 (6) | 0.0181 (5) | −0.0012 (4) | 0.0044 (4) | 0.0001 (5) |
N5 | 0.0225 (5) | 0.0153 (5) | 0.0154 (5) | 0.0005 (4) | 0.0063 (4) | −0.0017 (4) |
C1 | 0.0194 (6) | 0.0137 (6) | 0.0158 (6) | 0.0003 (5) | 0.0052 (5) | 0.0049 (5) |
C2 | 0.0203 (6) | 0.0123 (6) | 0.0143 (6) | −0.0016 (5) | 0.0031 (5) | 0.0026 (5) |
C3 | 0.0225 (6) | 0.0141 (6) | 0.0145 (6) | 0.0010 (5) | 0.0069 (5) | 0.0029 (5) |
C4 | 0.0181 (6) | 0.0172 (6) | 0.0150 (6) | 0.0002 (5) | 0.0045 (5) | 0.0045 (5) |
C5 | 0.0207 (6) | 0.0165 (6) | 0.0135 (6) | −0.0013 (5) | 0.0036 (5) | 0.0025 (5) |
C6 | 0.0213 (6) | 0.0145 (6) | 0.0145 (6) | 0.0000 (5) | 0.0060 (5) | 0.0016 (5) |
C7 | 0.0196 (6) | 0.0179 (6) | 0.0214 (7) | 0.0000 (5) | 0.0058 (5) | −0.0004 (5) |
C8 | 0.0254 (7) | 0.0261 (8) | 0.0303 (8) | −0.0017 (6) | 0.0121 (6) | 0.0027 (6) |
C9 | 0.0238 (7) | 0.0241 (7) | 0.0199 (7) | 0.0007 (5) | 0.0079 (5) | −0.0034 (6) |
C10 | 0.0371 (8) | 0.0227 (8) | 0.0425 (9) | 0.0041 (6) | 0.0144 (7) | −0.0069 (7) |
C11 | 0.0207 (6) | 0.0236 (7) | 0.0189 (6) | −0.0018 (5) | 0.0037 (5) | −0.0033 (6) |
C12 | 0.0301 (7) | 0.0345 (8) | 0.0177 (7) | −0.0014 (6) | 0.0004 (6) | −0.0021 (6) |
C13 | 0.0215 (6) | 0.0177 (6) | 0.0160 (6) | −0.0013 (5) | 0.0029 (5) | −0.0004 (5) |
C14 | 0.0196 (6) | 0.0229 (7) | 0.0126 (6) | 0.0000 (5) | 0.0059 (5) | −0.0015 (5) |
C15 | 0.0232 (7) | 0.0178 (7) | 0.0198 (6) | 0.0012 (5) | 0.0045 (5) | −0.0040 (5) |
C16 | 0.0238 (7) | 0.0239 (7) | 0.0235 (7) | −0.0014 (6) | 0.0028 (6) | −0.0058 (6) |
C17 | 0.0199 (6) | 0.0283 (8) | 0.0197 (7) | 0.0018 (5) | 0.0009 (5) | −0.0020 (6) |
C18 | 0.0229 (6) | 0.0239 (7) | 0.0153 (6) | 0.0018 (5) | 0.0068 (5) | −0.0001 (5) |
C19 | 0.0332 (8) | 0.0283 (9) | 0.0527 (10) | −0.0068 (7) | −0.0115 (8) | −0.0018 (8) |
C20 | 0.0313 (8) | 0.0271 (8) | 0.0244 (7) | 0.0014 (6) | 0.0052 (6) | 0.0053 (6) |
C21 | 0.0192 (6) | 0.0227 (7) | 0.0180 (6) | 0.0015 (5) | 0.0048 (5) | 0.0018 (5) |
C22 | 0.0169 (6) | 0.0230 (7) | 0.0160 (6) | −0.0008 (5) | 0.0024 (5) | −0.0014 (5) |
C23 | 0.0255 (7) | 0.0195 (7) | 0.0238 (7) | 0.0014 (5) | 0.0084 (6) | 0.0003 (6) |
C24 | 0.0278 (7) | 0.0245 (7) | 0.0241 (7) | −0.0009 (6) | 0.0101 (6) | 0.0014 (6) |
C25 | 0.0244 (7) | 0.0266 (7) | 0.0239 (7) | 0.0020 (6) | 0.0113 (6) | −0.0018 (6) |
C26 | 0.0232 (7) | 0.0229 (7) | 0.0183 (6) | 0.0009 (5) | 0.0048 (5) | −0.0025 (6) |
C27 | 0.0504 (10) | 0.0276 (8) | 0.0482 (10) | 0.0014 (7) | 0.0308 (9) | 0.0057 (7) |
C28 | 0.0370 (8) | 0.0240 (8) | 0.0341 (8) | 0.0038 (6) | 0.0158 (7) | 0.0005 (6) |
C29 | 0.0222 (6) | 0.0186 (7) | 0.0161 (6) | 0.0013 (5) | 0.0056 (5) | 0.0007 (5) |
C30 | 0.0229 (6) | 0.0160 (6) | 0.0200 (6) | 0.0002 (5) | 0.0081 (5) | −0.0019 (5) |
C31 | 0.0301 (7) | 0.0187 (7) | 0.0226 (7) | −0.0014 (5) | 0.0073 (6) | −0.0044 (6) |
C32 | 0.0512 (10) | 0.0353 (9) | 0.0255 (8) | −0.0077 (8) | 0.0172 (7) | −0.0105 (7) |
C33 | 0.0475 (9) | 0.0234 (8) | 0.0418 (9) | −0.0019 (7) | 0.0294 (8) | −0.0045 (7) |
C34 | 0.0253 (7) | 0.0215 (7) | 0.0252 (7) | −0.0002 (5) | 0.0119 (6) | −0.0005 (6) |
C35 | 0.0258 (7) | 0.0175 (7) | 0.0227 (7) | 0.0005 (5) | 0.0080 (6) | −0.0011 (5) |
O1W | 0.0275 (5) | 0.0216 (5) | 0.0202 (5) | −0.0052 (4) | 0.0084 (4) | −0.0029 (4) |
Geometric parameters (Å, º) top O1—C35 | 1.4275 (16) | C15—H15 | 0.9500 |
O1—H1A | 0.874 (9) | C16—C17 | 1.397 (2) |
N1—C14 | 1.3779 (16) | C16—C19 | 1.500 (2) |
N1—C13 | 1.4685 (17) | C17—C18 | 1.3837 (19) |
N1—H1 | 0.885 (9) | C17—H17 | 0.9500 |
N2—C14 | 1.3443 (17) | C18—C20 | 1.5076 (19) |
N2—C18 | 1.3451 (17) | C19—H19A | 0.9800 |
N3—C22 | 1.3705 (17) | C19—H19B | 0.9800 |
N3—C21 | 1.4558 (17) | C19—H19C | 0.9800 |
N3—H3 | 0.889 (9) | C20—H20A | 0.9800 |
N4—C22 | 1.3410 (17) | C20—H20B | 0.9800 |
N4—C26 | 1.3578 (17) | C20—H20C | 0.9800 |
N5—C29 | 1.4787 (16) | C21—H21A | 0.9900 |
N5—C30 | 1.4876 (16) | C21—H21B | 0.9900 |
N5—H5 | 0.896 (9) | C22—C23 | 1.4093 (19) |
C1—C6 | 1.4039 (17) | C23—C24 | 1.3744 (19) |
C1—C2 | 1.4080 (18) | C23—H23 | 0.9500 |
C1—C7 | 1.5243 (17) | C24—C25 | 1.401 (2) |
C2—C3 | 1.4041 (17) | C24—C27 | 1.506 (2) |
C2—C13 | 1.5155 (17) | C25—C26 | 1.377 (2) |
C3—C4 | 1.4067 (18) | C25—H25 | 0.9500 |
C3—C9 | 1.5177 (18) | C26—C28 | 1.5046 (19) |
C4—C5 | 1.4037 (18) | C27—H27A | 0.9800 |
C4—C21 | 1.5219 (17) | C27—H27B | 0.9800 |
C5—C6 | 1.4120 (17) | C27—H27C | 0.9800 |
C5—C11 | 1.5197 (17) | C28—H28A | 0.9800 |
C6—C29 | 1.5172 (18) | C28—H28B | 0.9800 |
C7—C8 | 1.5284 (19) | C28—H28C | 0.9800 |
C7—H7A | 0.9900 | C29—H29A | 0.9900 |
C7—H7B | 0.9900 | C29—H29B | 0.9900 |
C8—H8A | 0.9800 | C30—C35 | 1.5310 (18) |
C8—H8B | 0.9800 | C30—C31 | 1.5548 (18) |
C8—H8C | 0.9800 | C30—C34 | 1.5556 (18) |
C9—C10 | 1.532 (2) | C31—C32 | 1.531 (2) |
C9—H9A | 0.9900 | C31—H31A | 0.9900 |
C9—H9B | 0.9900 | C31—H31B | 0.9900 |
C10—H10A | 0.9800 | C32—C33 | 1.522 (2) |
C10—H10B | 0.9800 | C32—H32A | 0.9900 |
C10—H10C | 0.9800 | C32—H32B | 0.9900 |
C11—C12 | 1.5333 (19) | C33—C34 | 1.525 (2) |
C11—H11A | 0.9900 | C33—H33A | 0.9900 |
C11—H11B | 0.9900 | C33—H33B | 0.9900 |
C12—H12A | 0.9800 | C34—H34A | 0.9900 |
C12—H12B | 0.9800 | C34—H34B | 0.9900 |
C12—H12C | 0.9800 | C35—H35A | 0.9900 |
C13—H13A | 0.9900 | C35—H35B | 0.9900 |
C13—H13B | 0.9900 | O1W—H1W | 0.861 (9) |
C14—C15 | 1.4001 (18) | O1W—H2W | 0.871 (9) |
C15—C16 | 1.3824 (18) | | |
| | | |
C35—O1—H1A | 112.5 (13) | C16—C19—H19B | 109.5 |
C14—N1—C13 | 122.12 (11) | H19A—C19—H19B | 109.5 |
C14—N1—H1 | 112.4 (11) | C16—C19—H19C | 109.5 |
C13—N1—H1 | 114.0 (11) | H19A—C19—H19C | 109.5 |
C14—N2—C18 | 117.94 (11) | H19B—C19—H19C | 109.5 |
C22—N3—C21 | 125.38 (12) | C18—C20—H20A | 109.5 |
C22—N3—H3 | 116.6 (11) | C18—C20—H20B | 109.5 |
C21—N3—H3 | 116.7 (11) | H20A—C20—H20B | 109.5 |
C22—N4—C26 | 116.90 (11) | C18—C20—H20C | 109.5 |
C29—N5—C30 | 118.35 (10) | H20A—C20—H20C | 109.5 |
C29—N5—H5 | 108.8 (10) | H20B—C20—H20C | 109.5 |
C30—N5—H5 | 108.4 (10) | N3—C21—C4 | 109.97 (10) |
C6—C1—C2 | 119.53 (11) | N3—C21—H21A | 109.7 |
C6—C1—C7 | 120.77 (11) | C4—C21—H21A | 109.7 |
C2—C1—C7 | 119.70 (11) | N3—C21—H21B | 109.7 |
C3—C2—C1 | 120.72 (11) | C4—C21—H21B | 109.7 |
C3—C2—C13 | 120.66 (11) | H21A—C21—H21B | 108.2 |
C1—C2—C13 | 118.17 (11) | N4—C22—N3 | 118.97 (12) |
C2—C3—C4 | 119.15 (11) | N4—C22—C23 | 122.97 (12) |
C2—C3—C9 | 120.74 (11) | N3—C22—C23 | 118.03 (12) |
C4—C3—C9 | 120.10 (11) | C24—C23—C22 | 119.43 (13) |
C5—C4—C3 | 120.60 (11) | C24—C23—H23 | 120.3 |
C5—C4—C21 | 120.03 (11) | C22—C23—H23 | 120.3 |
C3—C4—C21 | 119.19 (11) | C23—C24—C25 | 117.79 (13) |
C4—C5—C6 | 119.53 (11) | C23—C24—C27 | 121.36 (13) |
C4—C5—C11 | 120.33 (11) | C25—C24—C27 | 120.85 (13) |
C6—C5—C11 | 120.12 (11) | C26—C25—C24 | 119.63 (12) |
C1—C6—C5 | 120.14 (11) | C26—C25—H25 | 120.2 |
C1—C6—C29 | 117.93 (11) | C24—C25—H25 | 120.2 |
C5—C6—C29 | 121.78 (11) | N4—C26—C25 | 123.26 (12) |
C1—C7—C8 | 111.59 (11) | N4—C26—C28 | 115.73 (12) |
C1—C7—H7A | 109.3 | C25—C26—C28 | 121.01 (12) |
C8—C7—H7A | 109.3 | C24—C27—H27A | 109.5 |
C1—C7—H7B | 109.3 | C24—C27—H27B | 109.5 |
C8—C7—H7B | 109.3 | H27A—C27—H27B | 109.5 |
H7A—C7—H7B | 108.0 | C24—C27—H27C | 109.5 |
C7—C8—H8A | 109.5 | H27A—C27—H27C | 109.5 |
C7—C8—H8B | 109.5 | H27B—C27—H27C | 109.5 |
H8A—C8—H8B | 109.5 | C26—C28—H28A | 109.5 |
C7—C8—H8C | 109.5 | C26—C28—H28B | 109.5 |
H8A—C8—H8C | 109.5 | H28A—C28—H28B | 109.5 |
H8B—C8—H8C | 109.5 | C26—C28—H28C | 109.5 |
C3—C9—C10 | 113.32 (11) | H28A—C28—H28C | 109.5 |
C3—C9—H9A | 108.9 | H28B—C28—H28C | 109.5 |
C10—C9—H9A | 108.9 | N5—C29—C6 | 108.41 (10) |
C3—C9—H9B | 108.9 | N5—C29—H29A | 110.0 |
C10—C9—H9B | 108.9 | C6—C29—H29A | 110.0 |
H9A—C9—H9B | 107.7 | N5—C29—H29B | 110.0 |
C9—C10—H10A | 109.5 | C6—C29—H29B | 110.0 |
C9—C10—H10B | 109.5 | H29A—C29—H29B | 108.4 |
H10A—C10—H10B | 109.5 | N5—C30—C35 | 106.05 (10) |
C9—C10—H10C | 109.5 | N5—C30—C31 | 110.47 (11) |
H10A—C10—H10C | 109.5 | C35—C30—C31 | 109.58 (11) |
H10B—C10—H10C | 109.5 | N5—C30—C34 | 116.39 (11) |
C5—C11—C12 | 113.62 (11) | C35—C30—C34 | 109.43 (11) |
C5—C11—H11A | 108.8 | C31—C30—C34 | 104.86 (10) |
C12—C11—H11A | 108.8 | C32—C31—C30 | 106.29 (11) |
C5—C11—H11B | 108.8 | C32—C31—H31A | 110.5 |
C12—C11—H11B | 108.8 | C30—C31—H31A | 110.5 |
H11A—C11—H11B | 107.7 | C32—C31—H31B | 110.5 |
C11—C12—H12A | 109.5 | C30—C31—H31B | 110.5 |
C11—C12—H12B | 109.5 | H31A—C31—H31B | 108.7 |
H12A—C12—H12B | 109.5 | C33—C32—C31 | 104.00 (12) |
C11—C12—H12C | 109.5 | C33—C32—H32A | 111.0 |
H12A—C12—H12C | 109.5 | C31—C32—H32A | 111.0 |
H12B—C12—H12C | 109.5 | C33—C32—H32B | 111.0 |
N1—C13—C2 | 106.75 (10) | C31—C32—H32B | 111.0 |
N1—C13—H13A | 110.4 | H32A—C32—H32B | 109.0 |
C2—C13—H13A | 110.4 | C32—C33—C34 | 103.01 (12) |
N1—C13—H13B | 110.4 | C32—C33—H33A | 111.2 |
C2—C13—H13B | 110.4 | C34—C33—H33A | 111.2 |
H13A—C13—H13B | 108.6 | C32—C33—H33B | 111.2 |
N2—C14—N1 | 115.60 (11) | C34—C33—H33B | 111.2 |
N2—C14—C15 | 122.67 (12) | H33A—C33—H33B | 109.1 |
N1—C14—C15 | 121.72 (12) | C33—C34—C30 | 104.58 (11) |
C16—C15—C14 | 119.04 (13) | C33—C34—H34A | 110.8 |
C16—C15—H15 | 120.5 | C30—C34—H34A | 110.8 |
C14—C15—H15 | 120.5 | C33—C34—H34B | 110.8 |
C15—C16—C17 | 118.19 (12) | C30—C34—H34B | 110.8 |
C15—C16—C19 | 120.87 (13) | H34A—C34—H34B | 108.9 |
C17—C16—C19 | 120.93 (13) | O1—C35—C30 | 113.25 (11) |
C18—C17—C16 | 119.44 (12) | O1—C35—H35A | 108.9 |
C18—C17—H17 | 120.3 | C30—C35—H35A | 108.9 |
C16—C17—H17 | 120.3 | O1—C35—H35B | 108.9 |
N2—C18—C17 | 122.67 (13) | C30—C35—H35B | 108.9 |
N2—C18—C20 | 115.89 (12) | H35A—C35—H35B | 107.7 |
C17—C18—C20 | 121.45 (12) | H1W—O1W—H2W | 107.2 (18) |
C16—C19—H19A | 109.5 | | |
| | | |
C6—C1—C2—C3 | 3.01 (18) | C15—C16—C17—C18 | −1.2 (2) |
C7—C1—C2—C3 | −176.05 (11) | C19—C16—C17—C18 | 177.68 (14) |
C6—C1—C2—C13 | −169.44 (11) | C14—N2—C18—C17 | 2.26 (18) |
C7—C1—C2—C13 | 11.50 (17) | C14—N2—C18—C20 | −177.50 (11) |
C1—C2—C3—C4 | 1.77 (18) | C16—C17—C18—N2 | −0.6 (2) |
C13—C2—C3—C4 | 174.02 (11) | C16—C17—C18—C20 | 179.14 (13) |
C1—C2—C3—C9 | −176.97 (11) | C22—N3—C21—C4 | −139.10 (13) |
C13—C2—C3—C9 | −4.72 (18) | C5—C4—C21—N3 | −84.62 (14) |
C2—C3—C4—C5 | −5.90 (18) | C3—C4—C21—N3 | 90.57 (14) |
C9—C3—C4—C5 | 172.84 (11) | C26—N4—C22—N3 | −178.80 (11) |
C2—C3—C4—C21 | 178.94 (11) | C26—N4—C22—C23 | −0.68 (18) |
C9—C3—C4—C21 | −2.32 (18) | C21—N3—C22—N4 | −0.42 (19) |
C3—C4—C5—C6 | 5.22 (18) | C21—N3—C22—C23 | −178.64 (12) |
C21—C4—C5—C6 | −179.67 (11) | N4—C22—C23—C24 | −0.8 (2) |
C3—C4—C5—C11 | −173.26 (11) | N3—C22—C23—C24 | 177.36 (12) |
C21—C4—C5—C11 | 1.85 (18) | C22—C23—C24—C25 | 1.3 (2) |
C2—C1—C6—C5 | −3.71 (18) | C22—C23—C24—C27 | −178.42 (14) |
C7—C1—C6—C5 | 175.34 (11) | C23—C24—C25—C26 | −0.4 (2) |
C2—C1—C6—C29 | 171.98 (11) | C27—C24—C25—C26 | 179.31 (14) |
C7—C1—C6—C29 | −8.97 (17) | C22—N4—C26—C25 | 1.63 (19) |
C4—C5—C6—C1 | −0.36 (18) | C22—N4—C26—C28 | −178.68 (12) |
C11—C5—C6—C1 | 178.12 (11) | C24—C25—C26—N4 | −1.1 (2) |
C4—C5—C6—C29 | −175.88 (11) | C24—C25—C26—C28 | 179.23 (13) |
C11—C5—C6—C29 | 2.60 (18) | C30—N5—C29—C6 | 168.54 (10) |
C6—C1—C7—C8 | −93.07 (14) | C1—C6—C29—N5 | −74.81 (14) |
C2—C1—C7—C8 | 85.97 (14) | C5—C6—C29—N5 | 100.80 (13) |
C2—C3—C9—C10 | −88.30 (15) | C29—N5—C30—C35 | −170.13 (10) |
C4—C3—C9—C10 | 92.98 (15) | C29—N5—C30—C31 | 71.21 (14) |
C4—C5—C11—C12 | −94.72 (14) | C29—N5—C30—C34 | −48.19 (15) |
C6—C5—C11—C12 | 86.81 (15) | N5—C30—C31—C32 | −122.98 (12) |
C14—N1—C13—C2 | −148.51 (12) | C35—C30—C31—C32 | 120.53 (13) |
C3—C2—C13—N1 | −95.00 (13) | C34—C30—C31—C32 | 3.17 (15) |
C1—C2—C13—N1 | 77.45 (14) | C30—C31—C32—C33 | −27.13 (16) |
C18—N2—C14—N1 | 177.18 (11) | C31—C32—C33—C34 | 40.92 (15) |
C18—N2—C14—C15 | −2.14 (18) | C32—C33—C34—C30 | −38.95 (15) |
C13—N1—C14—N2 | 154.81 (12) | N5—C30—C34—C33 | 144.32 (12) |
C13—N1—C14—C15 | −25.87 (18) | C35—C30—C34—C33 | −95.53 (13) |
N2—C14—C15—C16 | 0.36 (19) | C31—C30—C34—C33 | 21.93 (14) |
N1—C14—C15—C16 | −178.91 (12) | N5—C30—C35—O1 | 67.44 (13) |
C14—C15—C16—C17 | 1.31 (19) | C31—C30—C35—O1 | −173.32 (11) |
C14—C15—C16—C19 | −177.57 (14) | C34—C30—C35—O1 | −58.86 (14) |
Hydrogen-bond geometry (Å, º) topCg1 and Cg2 are the centroids of the C1–C6 and C14–C18/N2 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H2W···N5 | 0.87 (1) | 1.93 (1) | 2.8018 (14) | 175 (2) |
O1W—H1W···N2i | 0.86 (1) | 2.03 (1) | 2.8780 (15) | 166 (2) |
O1—H1A···O1Wi | 0.87 (1) | 1.83 (1) | 2.6993 (14) | 176 (2) |
N5—H5···O1Wi | 0.90 (1) | 2.52 (1) | 3.3302 (14) | 151 (1) |
N3—H3···O1i | 0.89 (1) | 2.05 (1) | 2.9115 (15) | 162 (2) |
N1—H1···O1Wi | 0.89 (1) | 2.50 (1) | 3.2618 (16) | 145 (1) |
C32—H32B···Cg1ii | 0.99 | 2.69 | 3.666 (2) | 169 |
C25—H25···Cg2iii | 0.95 | 2.84 | 3.728 (2) | 156 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z; (iii) x+1, y, z. |
{1-[(3,5-Bis{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzyl)amino]cyclopentyl}methanol methanol monosolvate (1b)
top Crystal data top C35H51N5O·CH4O | Z = 2 |
Mr = 589.85 | F(000) = 644 |
Triclinic, P1 | Dx = 1.046 Mg m−3 |
a = 12.1169 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.2380 (5) Å | Cell parameters from 9915 reflections |
c = 13.6258 (5) Å | θ = 2.8–30.5° |
α = 68.373 (2)° | µ = 0.07 mm−1 |
β = 79.379 (2)° | T = 100 K |
γ = 67.392 (2)° | Irregular, colourless |
V = 1873.32 (12) Å3 | 0.56 × 0.34 × 0.32 mm |
Data collection top Bruker X8 APEXII CCD diffractometer | Rint = 0.022 |
phi and ω scans | θmax = 26.4°, θmin = 1.8° |
32191 measured reflections | h = −14→15 |
7654 independent reflections | k = −15→16 |
5160 reflections with I > 2σ(I) | l = 0→17 |
Refinement top Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.184 | w = 1/[σ2(Fo2) + (0.026P)2 + 3.8856P] where P = (Fo2 + 2Fc2)/3 |
S = 1.21 | (Δ/σ)max < 0.001 |
7654 reflections | Δρmax = 0.64 e Å−3 |
410 parameters | Δρmin = −0.39 e Å−3 |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.27014 (18) | 0.57360 (19) | 0.78975 (18) | 0.0337 (5) | |
H1A | 1.3308 | 0.5159 | 0.7868 | 0.051* | |
N1 | 0.8131 (3) | 0.6398 (2) | 0.68505 (19) | 0.0298 (6) | |
H1 | 0.848 (3) | 0.588 (3) | 0.750 (3) | 0.030 (8)* | |
N2 | 0.7667 (3) | 0.6725 (3) | 0.5157 (2) | 0.0382 (7) | |
N3 | 0.6133 (2) | 0.73074 (19) | 1.09127 (18) | 0.0208 (5) | |
H3 | 0.656 (3) | 0.667 (3) | 1.081 (2) | 0.023 (8)* | |
N4 | 0.53696 (19) | 0.61277 (18) | 1.23326 (17) | 0.0182 (4) | |
N5 | 1.12190 (19) | 0.67304 (18) | 0.94010 (18) | 0.0190 (4) | |
H5 | 1.110 (3) | 0.628 (3) | 0.910 (3) | 0.027 (8)* | |
C1 | 0.9042 (2) | 0.7808 (2) | 0.78008 (19) | 0.0159 (5) | |
C2 | 0.7918 (2) | 0.7816 (2) | 0.76743 (19) | 0.0179 (5) | |
C3 | 0.6984 (2) | 0.7982 (2) | 0.8449 (2) | 0.0186 (5) | |
C4 | 0.7184 (2) | 0.8192 (2) | 0.93271 (19) | 0.0173 (5) | |
C5 | 0.8303 (2) | 0.8189 (2) | 0.94606 (19) | 0.0164 (5) | |
C6 | 0.9235 (2) | 0.7990 (2) | 0.86997 (19) | 0.0160 (5) | |
C7 | 1.0021 (2) | 0.7657 (2) | 0.6940 (2) | 0.0207 (5) | |
H7A | 0.9917 | 0.7167 | 0.6589 | 0.025* | |
H7B | 1.0809 | 0.7252 | 0.7264 | 0.025* | |
C8 | 1.0008 (3) | 0.8814 (2) | 0.6114 (2) | 0.0287 (6) | |
H8A | 0.9235 | 0.9212 | 0.5781 | 0.043* | |
H8B | 1.0652 | 0.8677 | 0.5575 | 0.043* | |
H8C | 1.0127 | 0.9296 | 0.6456 | 0.043* | |
C9 | 0.5782 (2) | 0.7944 (2) | 0.8331 (2) | 0.0249 (6) | |
H9A | 0.5417 | 0.7656 | 0.9043 | 0.030* | |
H9B | 0.5909 | 0.7389 | 0.7960 | 0.030* | |
C10 | 0.4912 (3) | 0.9125 (3) | 0.7722 (3) | 0.0349 (7) | |
H10A | 0.4798 | 0.9686 | 0.8075 | 0.052* | |
H10B | 0.4141 | 0.9056 | 0.7701 | 0.052* | |
H10C | 0.5241 | 0.9391 | 0.6999 | 0.052* | |
C11 | 0.8503 (2) | 0.8411 (2) | 1.0417 (2) | 0.0195 (5) | |
H11A | 0.9340 | 0.7959 | 1.0622 | 0.023* | |
H11B | 0.7971 | 0.8138 | 1.1016 | 0.023* | |
C12 | 0.8259 (3) | 0.9694 (2) | 1.0213 (2) | 0.0283 (6) | |
H12A | 0.8792 | 0.9967 | 0.9628 | 0.042* | |
H12B | 0.8406 | 0.9791 | 1.0851 | 0.042* | |
H12C | 0.7425 | 1.0144 | 1.0030 | 0.042* | |
C13 | 0.7709 (3) | 0.7627 (2) | 0.6698 (2) | 0.0240 (6) | |
H13A | 0.6844 | 0.7971 | 0.6565 | 0.029* | |
H13B | 0.8140 | 0.8016 | 0.6074 | 0.029* | |
C14 | 0.8157 (3) | 0.5977 (3) | 0.6068 (2) | 0.0301 (7) | |
C15 | 0.8695 (3) | 0.4779 (3) | 0.6252 (3) | 0.0351 (7) | |
H15 | 0.9032 | 0.4270 | 0.6910 | 0.042* | |
C16 | 0.8722 (3) | 0.4360 (4) | 0.5462 (3) | 0.0480 (10) | |
C17 | 0.8216 (4) | 0.5129 (4) | 0.4515 (3) | 0.0548 (12) | |
H17 | 0.8222 | 0.4854 | 0.3960 | 0.066* | |
C18 | 0.7710 (3) | 0.6284 (4) | 0.4385 (3) | 0.0516 (11) | |
C19 | 0.9332 (4) | 0.3088 (4) | 0.5622 (4) | 0.0662 (14) | |
H19A | 0.8931 | 0.2853 | 0.5225 | 0.099* | |
H19B | 0.9289 | 0.2646 | 0.6375 | 0.099* | |
H19C | 1.0172 | 0.2936 | 0.5368 | 0.099* | |
C20 | 0.7149 (5) | 0.7156 (5) | 0.3377 (3) | 0.0755 (16) | |
H20A | 0.6293 | 0.7531 | 0.3520 | 0.113* | |
H20B | 0.7252 | 0.6763 | 0.2863 | 0.113* | |
H20C | 0.7535 | 0.7741 | 0.3089 | 0.113* | |
C21 | 0.6162 (2) | 0.8401 (2) | 1.0146 (2) | 0.0200 (5) | |
H21A | 0.6267 | 0.8879 | 1.0510 | 0.024* | |
H21B | 0.5393 | 0.8828 | 0.9791 | 0.024* | |
C22 | 0.5286 (2) | 0.7214 (2) | 1.17214 (19) | 0.0168 (5) | |
C23 | 0.4398 (2) | 0.8186 (2) | 1.1916 (2) | 0.0183 (5) | |
H23 | 0.4344 | 0.8945 | 1.1460 | 0.022* | |
C24 | 0.3604 (2) | 0.8028 (2) | 1.2778 (2) | 0.0206 (5) | |
C25 | 0.3712 (2) | 0.6901 (2) | 1.3418 (2) | 0.0226 (5) | |
H25 | 0.3185 | 0.6767 | 1.4022 | 0.027* | |
C26 | 0.4592 (2) | 0.5973 (2) | 1.3170 (2) | 0.0211 (5) | |
C27 | 0.2644 (3) | 0.9050 (2) | 1.3014 (2) | 0.0293 (6) | |
H27A | 0.2900 | 0.9726 | 1.2716 | 0.044* | |
H27B | 0.2505 | 0.8873 | 1.3781 | 0.044* | |
H27C | 0.1902 | 0.9218 | 1.2698 | 0.044* | |
C28 | 0.4714 (3) | 0.4746 (2) | 1.3806 (2) | 0.0282 (6) | |
H28A | 0.4429 | 0.4419 | 1.3406 | 0.042* | |
H28B | 0.4236 | 0.4724 | 1.4472 | 0.042* | |
H28C | 0.5556 | 0.4291 | 1.3956 | 0.042* | |
C29 | 1.0471 (2) | 0.7940 (2) | 0.8843 (2) | 0.0191 (5) | |
H29A | 1.0858 | 0.8231 | 0.8144 | 0.023* | |
H29B | 1.0398 | 0.8442 | 0.9257 | 0.023* | |
C30 | 1.2540 (2) | 0.6488 (2) | 0.9314 (2) | 0.0212 (5) | |
C31 | 1.2823 (2) | 0.7329 (2) | 0.9663 (2) | 0.0277 (6) | |
H31A | 1.3654 | 0.7311 | 0.9441 | 0.033* | |
H31B | 1.2264 | 0.8130 | 0.9367 | 0.033* | |
C32 | 1.2660 (3) | 0.6884 (3) | 1.0860 (3) | 0.0313 (7) | |
H32A | 1.1801 | 0.7099 | 1.1090 | 0.038* | |
H32B | 1.3061 | 0.7192 | 1.1194 | 0.038* | |
C33 | 1.3256 (3) | 0.5566 (3) | 1.1131 (2) | 0.0308 (6) | |
H33A | 1.2857 | 0.5159 | 1.1770 | 0.037* | |
H33B | 1.4113 | 0.5318 | 1.1261 | 0.037* | |
C34 | 1.3113 (2) | 0.5300 (2) | 1.0158 (2) | 0.0265 (6) | |
H34A | 1.2590 | 0.4830 | 1.0346 | 0.032* | |
H34B | 1.3901 | 0.4868 | 0.9889 | 0.032* | |
C35 | 1.3038 (2) | 0.6496 (2) | 0.8197 (2) | 0.0270 (6) | |
H35A | 1.2728 | 0.7292 | 0.7694 | 0.032* | |
H35B | 1.3922 | 0.6249 | 0.8170 | 0.032* | |
O1A | 0.95054 (19) | 0.4462 (2) | 0.85754 (17) | 0.0358 (5) | |
H1AA | 0.9330 | 0.4031 | 0.9162 | 0.054* | |
C1A | 1.0583 (3) | 0.4590 (3) | 0.8631 (2) | 0.0296 (6) | |
H1A1 | 1.0627 | 0.5308 | 0.8087 | 0.044* | |
H1A2 | 1.1256 | 0.3929 | 0.8515 | 0.044* | |
H1A3 | 1.0623 | 0.4622 | 0.9331 | 0.044* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0203 (10) | 0.0337 (12) | 0.0483 (13) | 0.0011 (9) | 0.0023 (9) | −0.0275 (11) |
N1 | 0.0507 (16) | 0.0266 (13) | 0.0192 (12) | −0.0167 (12) | −0.0054 (11) | −0.0102 (10) |
N2 | 0.0466 (16) | 0.0630 (19) | 0.0195 (12) | −0.0329 (15) | −0.0007 (11) | −0.0154 (12) |
N3 | 0.0201 (11) | 0.0157 (11) | 0.0223 (11) | −0.0041 (9) | 0.0068 (9) | −0.0074 (9) |
N4 | 0.0167 (10) | 0.0180 (10) | 0.0200 (11) | −0.0060 (8) | 0.0019 (8) | −0.0075 (9) |
N5 | 0.0153 (10) | 0.0168 (10) | 0.0252 (11) | −0.0034 (8) | −0.0012 (8) | −0.0094 (9) |
C1 | 0.0184 (12) | 0.0112 (11) | 0.0143 (11) | −0.0024 (9) | 0.0019 (9) | −0.0041 (9) |
C2 | 0.0222 (13) | 0.0144 (11) | 0.0149 (12) | −0.0045 (10) | −0.0027 (10) | −0.0035 (9) |
C3 | 0.0196 (12) | 0.0133 (11) | 0.0198 (12) | −0.0042 (9) | −0.0008 (10) | −0.0036 (10) |
C4 | 0.0175 (12) | 0.0149 (11) | 0.0170 (12) | −0.0053 (9) | 0.0017 (9) | −0.0039 (9) |
C5 | 0.0186 (12) | 0.0140 (11) | 0.0151 (11) | −0.0034 (9) | 0.0004 (9) | −0.0061 (9) |
C6 | 0.0150 (12) | 0.0119 (11) | 0.0194 (12) | −0.0028 (9) | −0.0002 (9) | −0.0058 (9) |
C7 | 0.0214 (13) | 0.0223 (13) | 0.0177 (12) | −0.0066 (10) | 0.0038 (10) | −0.0090 (10) |
C8 | 0.0338 (16) | 0.0219 (14) | 0.0242 (14) | −0.0081 (12) | 0.0097 (12) | −0.0076 (11) |
C9 | 0.0213 (13) | 0.0315 (15) | 0.0254 (14) | −0.0139 (11) | −0.0010 (11) | −0.0082 (12) |
C10 | 0.0247 (15) | 0.0402 (18) | 0.0346 (17) | −0.0095 (13) | −0.0074 (12) | −0.0057 (14) |
C11 | 0.0220 (13) | 0.0199 (13) | 0.0175 (12) | −0.0054 (10) | 0.0007 (10) | −0.0097 (10) |
C12 | 0.0347 (16) | 0.0196 (13) | 0.0317 (15) | −0.0048 (12) | −0.0030 (12) | −0.0140 (12) |
C13 | 0.0304 (15) | 0.0230 (13) | 0.0194 (13) | −0.0114 (11) | −0.0015 (11) | −0.0056 (11) |
C14 | 0.0360 (16) | 0.0473 (18) | 0.0230 (14) | −0.0286 (14) | 0.0079 (12) | −0.0184 (13) |
C15 | 0.0389 (17) | 0.0447 (18) | 0.0386 (17) | −0.0292 (15) | 0.0183 (14) | −0.0265 (15) |
C16 | 0.046 (2) | 0.077 (3) | 0.056 (2) | −0.045 (2) | 0.0341 (18) | −0.053 (2) |
C17 | 0.060 (2) | 0.110 (4) | 0.044 (2) | −0.065 (3) | 0.0349 (18) | −0.060 (2) |
C18 | 0.051 (2) | 0.110 (4) | 0.0274 (17) | −0.058 (2) | 0.0143 (15) | −0.037 (2) |
C19 | 0.066 (3) | 0.088 (3) | 0.089 (3) | −0.052 (3) | 0.052 (2) | −0.078 (3) |
C20 | 0.083 (3) | 0.142 (5) | 0.030 (2) | −0.066 (3) | 0.001 (2) | −0.033 (3) |
C21 | 0.0188 (12) | 0.0170 (12) | 0.0203 (13) | −0.0051 (10) | 0.0046 (10) | −0.0059 (10) |
C22 | 0.0153 (12) | 0.0199 (12) | 0.0182 (12) | −0.0060 (10) | −0.0002 (9) | −0.0098 (10) |
C23 | 0.0166 (12) | 0.0162 (12) | 0.0192 (12) | −0.0034 (9) | 0.0013 (9) | −0.0061 (10) |
C24 | 0.0185 (12) | 0.0226 (13) | 0.0210 (13) | −0.0063 (10) | 0.0041 (10) | −0.0110 (11) |
C25 | 0.0180 (12) | 0.0250 (14) | 0.0232 (13) | −0.0073 (11) | 0.0057 (10) | −0.0092 (11) |
C26 | 0.0188 (13) | 0.0207 (13) | 0.0228 (13) | −0.0074 (10) | 0.0020 (10) | −0.0069 (11) |
C27 | 0.0268 (14) | 0.0202 (13) | 0.0314 (15) | −0.0023 (11) | 0.0117 (12) | −0.0106 (12) |
C28 | 0.0314 (15) | 0.0211 (14) | 0.0270 (14) | −0.0098 (12) | 0.0087 (12) | −0.0064 (11) |
C29 | 0.0200 (12) | 0.0168 (12) | 0.0214 (13) | −0.0070 (10) | 0.0031 (10) | −0.0085 (10) |
C30 | 0.0147 (12) | 0.0198 (13) | 0.0309 (14) | −0.0070 (10) | 0.0028 (10) | −0.0111 (11) |
C31 | 0.0189 (13) | 0.0237 (14) | 0.0447 (17) | −0.0077 (11) | −0.0020 (12) | −0.0152 (13) |
C32 | 0.0240 (14) | 0.0360 (16) | 0.0426 (18) | −0.0095 (12) | −0.0047 (13) | −0.0219 (14) |
C33 | 0.0241 (14) | 0.0330 (16) | 0.0354 (16) | −0.0110 (12) | −0.0023 (12) | −0.0097 (13) |
C34 | 0.0197 (13) | 0.0242 (14) | 0.0348 (16) | −0.0058 (11) | 0.0008 (11) | −0.0116 (12) |
C35 | 0.0168 (13) | 0.0254 (14) | 0.0356 (16) | −0.0063 (11) | 0.0066 (11) | −0.0114 (12) |
O1A | 0.0292 (11) | 0.0375 (12) | 0.0312 (11) | −0.0152 (9) | −0.0019 (9) | 0.0033 (9) |
C1A | 0.0297 (15) | 0.0257 (14) | 0.0330 (16) | −0.0124 (12) | 0.0041 (12) | −0.0089 (12) |
Geometric parameters (Å, º) top O1—C35 | 1.423 (4) | C16—C17 | 1.386 (6) |
O1—H1A | 0.8400 | C16—C19 | 1.503 (6) |
N1—C14 | 1.364 (4) | C17—C18 | 1.366 (6) |
N1—C13 | 1.451 (4) | C17—H17 | 0.9500 |
N1—H1 | 0.94 (3) | C18—C20 | 1.501 (6) |
N2—C14 | 1.337 (4) | C19—H19A | 0.9800 |
N2—C18 | 1.363 (4) | C19—H19B | 0.9800 |
N3—C22 | 1.365 (3) | C19—H19C | 0.9800 |
N3—C21 | 1.448 (3) | C20—H20A | 0.9800 |
N3—H3 | 0.85 (3) | C20—H20B | 0.9800 |
N4—C22 | 1.345 (3) | C20—H20C | 0.9800 |
N4—C26 | 1.346 (3) | C21—H21A | 0.9900 |
N5—C29 | 1.485 (3) | C21—H21B | 0.9900 |
N5—C30 | 1.497 (3) | C22—C23 | 1.402 (3) |
N5—H5 | 0.90 (3) | C23—C24 | 1.381 (3) |
C1—C2 | 1.400 (4) | C23—H23 | 0.9500 |
C1—C6 | 1.407 (3) | C24—C25 | 1.391 (4) |
C1—C7 | 1.517 (3) | C24—C27 | 1.503 (3) |
C2—C3 | 1.408 (3) | C25—C26 | 1.388 (4) |
C2—C13 | 1.522 (3) | C25—H25 | 0.9500 |
C3—C4 | 1.404 (4) | C26—C28 | 1.495 (4) |
C3—C9 | 1.517 (4) | C27—H27A | 0.9800 |
C4—C5 | 1.398 (3) | C27—H27B | 0.9800 |
C4—C21 | 1.520 (3) | C27—H27C | 0.9800 |
C5—C6 | 1.401 (3) | C28—H28A | 0.9800 |
C5—C11 | 1.515 (3) | C28—H28B | 0.9800 |
C6—C29 | 1.518 (3) | C28—H28C | 0.9800 |
C7—C8 | 1.526 (4) | C29—H29A | 0.9900 |
C7—H7A | 0.9900 | C29—H29B | 0.9900 |
C7—H7B | 0.9900 | C30—C31 | 1.525 (4) |
C8—H8A | 0.9800 | C30—C35 | 1.527 (4) |
C8—H8B | 0.9800 | C30—C34 | 1.549 (4) |
C8—H8C | 0.9800 | C31—C32 | 1.519 (4) |
C9—C10 | 1.531 (4) | C31—H31A | 0.9900 |
C9—H9A | 0.9900 | C31—H31B | 0.9900 |
C9—H9B | 0.9900 | C32—C33 | 1.536 (4) |
C10—H10A | 0.9800 | C32—H32A | 0.9900 |
C10—H10B | 0.9800 | C32—H32B | 0.9900 |
C10—H10C | 0.9800 | C33—C34 | 1.545 (4) |
C11—C12 | 1.531 (4) | C33—H33A | 0.9900 |
C11—H11A | 0.9900 | C33—H33B | 0.9900 |
C11—H11B | 0.9900 | C34—H34A | 0.9900 |
C12—H12A | 0.9800 | C34—H34B | 0.9900 |
C12—H12B | 0.9800 | C35—H35A | 0.9900 |
C12—H12C | 0.9800 | C35—H35B | 0.9900 |
C13—H13A | 0.9900 | O1A—C1A | 1.399 (4) |
C13—H13B | 0.9900 | O1A—H1AA | 0.8400 |
C14—C15 | 1.406 (5) | C1A—H1A1 | 0.9800 |
C15—C16 | 1.371 (4) | C1A—H1A2 | 0.9800 |
C15—H15 | 0.9500 | C1A—H1A3 | 0.9800 |
| | | |
C35—O1—H1A | 109.5 | H19A—C19—H19C | 109.5 |
C14—N1—C13 | 122.7 (3) | H19B—C19—H19C | 109.5 |
C14—N1—H1 | 119 (2) | C18—C20—H20A | 109.5 |
C13—N1—H1 | 118 (2) | C18—C20—H20B | 109.5 |
C14—N2—C18 | 117.3 (3) | H20A—C20—H20B | 109.5 |
C22—N3—C21 | 123.8 (2) | C18—C20—H20C | 109.5 |
C22—N3—H3 | 114 (2) | H20A—C20—H20C | 109.5 |
C21—N3—H3 | 121 (2) | H20B—C20—H20C | 109.5 |
C22—N4—C26 | 118.8 (2) | N3—C21—C4 | 110.2 (2) |
C29—N5—C30 | 115.6 (2) | N3—C21—H21A | 109.6 |
C29—N5—H5 | 106 (2) | C4—C21—H21A | 109.6 |
C30—N5—H5 | 106 (2) | N3—C21—H21B | 109.6 |
C2—C1—C6 | 119.8 (2) | C4—C21—H21B | 109.6 |
C2—C1—C7 | 119.4 (2) | H21A—C21—H21B | 108.1 |
C6—C1—C7 | 120.7 (2) | N4—C22—N3 | 115.6 (2) |
C1—C2—C3 | 120.5 (2) | N4—C22—C23 | 122.0 (2) |
C1—C2—C13 | 119.7 (2) | N3—C22—C23 | 122.3 (2) |
C3—C2—C13 | 119.8 (2) | C24—C23—C22 | 119.2 (2) |
C4—C3—C2 | 118.8 (2) | C24—C23—H23 | 120.4 |
C4—C3—C9 | 120.7 (2) | C22—C23—H23 | 120.4 |
C2—C3—C9 | 120.5 (2) | C23—C24—C25 | 118.4 (2) |
C5—C4—C3 | 121.1 (2) | C23—C24—C27 | 120.6 (2) |
C5—C4—C21 | 120.5 (2) | C25—C24—C27 | 121.0 (2) |
C3—C4—C21 | 118.4 (2) | C26—C25—C24 | 119.8 (2) |
C4—C5—C6 | 119.6 (2) | C26—C25—H25 | 120.1 |
C4—C5—C11 | 120.3 (2) | C24—C25—H25 | 120.1 |
C6—C5—C11 | 120.1 (2) | N4—C26—C25 | 121.9 (2) |
C5—C6—C1 | 120.1 (2) | N4—C26—C28 | 116.3 (2) |
C5—C6—C29 | 120.7 (2) | C25—C26—C28 | 121.8 (2) |
C1—C6—C29 | 119.2 (2) | C24—C27—H27A | 109.5 |
C1—C7—C8 | 112.1 (2) | C24—C27—H27B | 109.5 |
C1—C7—H7A | 109.2 | H27A—C27—H27B | 109.5 |
C8—C7—H7A | 109.2 | C24—C27—H27C | 109.5 |
C1—C7—H7B | 109.2 | H27A—C27—H27C | 109.5 |
C8—C7—H7B | 109.2 | H27B—C27—H27C | 109.5 |
H7A—C7—H7B | 107.9 | C26—C28—H28A | 109.5 |
C7—C8—H8A | 109.5 | C26—C28—H28B | 109.5 |
C7—C8—H8B | 109.5 | H28A—C28—H28B | 109.5 |
H8A—C8—H8B | 109.5 | C26—C28—H28C | 109.5 |
C7—C8—H8C | 109.5 | H28A—C28—H28C | 109.5 |
H8A—C8—H8C | 109.5 | H28B—C28—H28C | 109.5 |
H8B—C8—H8C | 109.5 | N5—C29—C6 | 110.1 (2) |
C3—C9—C10 | 113.1 (2) | N5—C29—H29A | 109.6 |
C3—C9—H9A | 109.0 | C6—C29—H29A | 109.6 |
C10—C9—H9A | 109.0 | N5—C29—H29B | 109.6 |
C3—C9—H9B | 109.0 | C6—C29—H29B | 109.6 |
C10—C9—H9B | 109.0 | H29A—C29—H29B | 108.1 |
H9A—C9—H9B | 107.8 | N5—C30—C31 | 110.6 (2) |
C9—C10—H10A | 109.5 | N5—C30—C35 | 110.3 (2) |
C9—C10—H10B | 109.5 | C31—C30—C35 | 113.0 (2) |
H10A—C10—H10B | 109.5 | N5—C30—C34 | 107.1 (2) |
C9—C10—H10C | 109.5 | C31—C30—C34 | 103.3 (2) |
H10A—C10—H10C | 109.5 | C35—C30—C34 | 112.1 (2) |
H10B—C10—H10C | 109.5 | C32—C31—C30 | 103.5 (2) |
C5—C11—C12 | 112.6 (2) | C32—C31—H31A | 111.1 |
C5—C11—H11A | 109.1 | C30—C31—H31A | 111.1 |
C12—C11—H11A | 109.1 | C32—C31—H31B | 111.1 |
C5—C11—H11B | 109.1 | C30—C31—H31B | 111.1 |
C12—C11—H11B | 109.1 | H31A—C31—H31B | 109.0 |
H11A—C11—H11B | 107.8 | C31—C32—C33 | 103.2 (2) |
C11—C12—H12A | 109.5 | C31—C32—H32A | 111.1 |
C11—C12—H12B | 109.5 | C33—C32—H32A | 111.1 |
H12A—C12—H12B | 109.5 | C31—C32—H32B | 111.1 |
C11—C12—H12C | 109.5 | C33—C32—H32B | 111.1 |
H12A—C12—H12C | 109.5 | H32A—C32—H32B | 109.1 |
H12B—C12—H12C | 109.5 | C32—C33—C34 | 105.5 (2) |
N1—C13—C2 | 109.9 (2) | C32—C33—H33A | 110.6 |
N1—C13—H13A | 109.7 | C34—C33—H33A | 110.6 |
C2—C13—H13A | 109.7 | C32—C33—H33B | 110.6 |
N1—C13—H13B | 109.7 | C34—C33—H33B | 110.6 |
C2—C13—H13B | 109.7 | H33A—C33—H33B | 108.8 |
H13A—C13—H13B | 108.2 | C33—C34—C30 | 106.2 (2) |
N2—C14—N1 | 118.4 (3) | C33—C34—H34A | 110.5 |
N2—C14—C15 | 122.8 (3) | C30—C34—H34A | 110.5 |
N1—C14—C15 | 118.8 (3) | C33—C34—H34B | 110.5 |
C16—C15—C14 | 118.6 (4) | C30—C34—H34B | 110.5 |
C16—C15—H15 | 120.7 | H34A—C34—H34B | 108.7 |
C14—C15—H15 | 120.7 | O1—C35—C30 | 110.5 (2) |
C15—C16—C17 | 119.0 (4) | O1—C35—H35A | 109.5 |
C15—C16—C19 | 119.8 (4) | C30—C35—H35A | 109.5 |
C17—C16—C19 | 121.2 (3) | O1—C35—H35B | 109.5 |
C18—C17—C16 | 119.6 (3) | C30—C35—H35B | 109.5 |
C18—C17—H17 | 120.2 | H35A—C35—H35B | 108.1 |
C16—C17—H17 | 120.2 | C1A—O1A—H1AA | 109.5 |
N2—C18—C17 | 122.7 (4) | O1A—C1A—H1A1 | 109.5 |
N2—C18—C20 | 115.5 (4) | O1A—C1A—H1A2 | 109.5 |
C17—C18—C20 | 121.8 (4) | H1A1—C1A—H1A2 | 109.5 |
C16—C19—H19A | 109.5 | O1A—C1A—H1A3 | 109.5 |
C16—C19—H19B | 109.5 | H1A1—C1A—H1A3 | 109.5 |
H19A—C19—H19B | 109.5 | H1A2—C1A—H1A3 | 109.5 |
C16—C19—H19C | 109.5 | | |
| | | |
C6—C1—C2—C3 | −1.2 (4) | C15—C16—C17—C18 | 0.4 (5) |
C7—C1—C2—C3 | −178.5 (2) | C19—C16—C17—C18 | −177.6 (3) |
C6—C1—C2—C13 | 179.5 (2) | C14—N2—C18—C17 | 0.6 (5) |
C7—C1—C2—C13 | 2.3 (3) | C14—N2—C18—C20 | 180.0 (3) |
C1—C2—C3—C4 | 2.8 (4) | C16—C17—C18—N2 | −0.6 (5) |
C13—C2—C3—C4 | −177.9 (2) | C16—C17—C18—C20 | −180.0 (3) |
C1—C2—C3—C9 | −177.7 (2) | C22—N3—C21—C4 | −177.5 (2) |
C13—C2—C3—C9 | 1.6 (4) | C5—C4—C21—N3 | −93.1 (3) |
C2—C3—C4—C5 | −2.7 (4) | C3—C4—C21—N3 | 85.7 (3) |
C9—C3—C4—C5 | 177.8 (2) | C26—N4—C22—N3 | 177.4 (2) |
C2—C3—C4—C21 | 178.5 (2) | C26—N4—C22—C23 | −1.5 (4) |
C9—C3—C4—C21 | −1.0 (3) | C21—N3—C22—N4 | 177.4 (2) |
C3—C4—C5—C6 | 1.0 (4) | C21—N3—C22—C23 | −3.7 (4) |
C21—C4—C5—C6 | 179.7 (2) | N4—C22—C23—C24 | 1.8 (4) |
C3—C4—C5—C11 | −179.6 (2) | N3—C22—C23—C24 | −177.0 (2) |
C21—C4—C5—C11 | −0.9 (3) | C22—C23—C24—C25 | −0.5 (4) |
C4—C5—C6—C1 | 0.7 (4) | C22—C23—C24—C27 | 179.7 (3) |
C11—C5—C6—C1 | −178.7 (2) | C23—C24—C25—C26 | −0.9 (4) |
C4—C5—C6—C29 | −177.8 (2) | C27—C24—C25—C26 | 178.8 (3) |
C11—C5—C6—C29 | 2.8 (3) | C22—N4—C26—C25 | 0.0 (4) |
C2—C1—C6—C5 | −0.6 (3) | C22—N4—C26—C28 | 178.8 (2) |
C7—C1—C6—C5 | 176.6 (2) | C24—C25—C26—N4 | 1.3 (4) |
C2—C1—C6—C29 | 178.0 (2) | C24—C25—C26—C28 | −177.5 (3) |
C7—C1—C6—C29 | −4.8 (3) | C30—N5—C29—C6 | 162.4 (2) |
C2—C1—C7—C8 | 89.8 (3) | C5—C6—C29—N5 | 90.9 (3) |
C6—C1—C7—C8 | −87.4 (3) | C1—C6—C29—N5 | −87.6 (3) |
C4—C3—C9—C10 | 90.5 (3) | C29—N5—C30—C31 | 54.1 (3) |
C2—C3—C9—C10 | −89.0 (3) | C29—N5—C30—C35 | −71.7 (3) |
C4—C5—C11—C12 | −91.6 (3) | C29—N5—C30—C34 | 166.1 (2) |
C6—C5—C11—C12 | 87.8 (3) | N5—C30—C31—C32 | 75.2 (3) |
C14—N1—C13—C2 | −173.9 (3) | C35—C30—C31—C32 | −160.5 (2) |
C1—C2—C13—N1 | 83.0 (3) | C34—C30—C31—C32 | −39.2 (3) |
C3—C2—C13—N1 | −96.2 (3) | C30—C31—C32—C33 | 42.6 (3) |
C18—N2—C14—N1 | 179.7 (3) | C31—C32—C33—C34 | −29.1 (3) |
C18—N2—C14—C15 | −0.4 (4) | C32—C33—C34—C30 | 5.1 (3) |
C13—N1—C14—N2 | −6.6 (4) | N5—C30—C34—C33 | −96.1 (2) |
C13—N1—C14—C15 | 173.5 (3) | C31—C30—C34—C33 | 20.7 (3) |
N2—C14—C15—C16 | 0.3 (4) | C35—C30—C34—C33 | 142.8 (2) |
N1—C14—C15—C16 | −179.8 (3) | N5—C30—C35—O1 | −52.9 (3) |
C14—C15—C16—C17 | −0.3 (4) | C31—C30—C35—O1 | −177.4 (2) |
C14—C15—C16—C19 | 177.8 (3) | C34—C30—C35—O1 | 66.3 (3) |
Hydrogen-bond geometry (Å, º) topCg1 and Cg3 are the centroids of the C1–C6 and C22–C26/N4 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1A | 0.94 (3) | 2.01 (3) | 2.930 (3) | 162 (2) |
C15—H15···O1A | 0.95 | 2.56 | 3.318 (3) | 137 |
N5—H5···O1 | 0.90 (3) | 2.36 (3) | 2.823 (3) | 112 (2) |
O1—H1A···N4i | 0.84 | 1.90 | 2.741 (3) | 174 |
O1A—H1AA···N5i | 0.84 | 1.97 | 2.798 (3) | 170 |
C27—H27A···Cg1ii | 0.98 | 2.67 | 3.541 (3) | 148 |
C32—H32B···Cg3iii | 0.98 | 2.69 | 3.614 (3) | 156 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+2, −z+2; (iii) x+1, y, z. |
Acknowledgements
Open-access funding was provided by the Publication Fund of the TU Bergakademie Freiberg.
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