research communications
R,2S,5R)-2-isopropyl-5-methylcyclohexyl] 2-methyl (2S,4S,5R)-1-[(2S,3R,5R)-5-methoxycarbonyl-2-(2-methylphenyl)pyrrolidine-3-carbonyl]-5-(2-methylphenyl)pyrrolidine-2,4-dicarboxylate
of 4-[(1aDepartment of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation, and bInstitute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, Moscow 119991, Russian Federation
*Correspondence e-mail: kudr@med.chem.msu.ru
The title compound, C38H50N2O7, represents a chiral β-proline dipeptide. Corresponding stereogenic centres of constituting pyrrolidine units have opposite absolute configurations. The central amide fragment is planar within 0.1 Å and adopts a Z configuration along the N—CO bond. In the crystal, the hydrogen atoms of the methylene groups form several short intermolecular C—H⋯O contacts with the carbonyl oxygen atoms of an adjacent molecule. The only active amino hydrogen atom is not involved in hydrogen bonding.
CCDC reference: 1905705
1. Chemical context
We have developed an asymmetric protecting-group-free method for the efficient synthesis of alternating β-proline utilizing the stereospecific cycloaddition of non-racemic homochiral acrylamides to (Kudryavtsev et al., 2013, 2015b). Several members of this novel β-peptide class display cell-cycle-directed antiproliferative activity in hormone-refractory prostate cancer cells (Kudryavtsev et al., 2015a,b; 2016). The preference for the Z configuration of β-amide bonds in alternating β-proline was explained by interaction between a lone pair of the carbonyl oxygen atom of the β-amide group and a vacant π* orbital of C∊ of the methoxycarbonyl groups (Kudryavtsev et al., 2015b).
2. Structural commentary
The title compound (Fig. 1) is a chiral dimeric β-proline derivative. The central amide fragment C4,C1,N1,C18,O5,C20 is planar within 0.1 Å and adopts a Z configuration along the N—CO bond. The Z/E or trans/cis configuration of a peptide bond is assigned by IUPAC rules due to its partial double-bond character (IUPAC–IUB, 1970). The amino N2 atom is clearly trigonal–pyramidal with C—N—C and C—N—H bond angles varying from 104.4 (4) to 112 (4)°. Both pyrrolidine rings possess envelope conformations with flap atoms C3 and C19. These atoms deviate from the basal planes of the envelopes by 0.582 (7) and 0.524 Å, respectively. In contrast to the previously reported structures of β-proline oligomers, the flap atoms C3 and C19 are not connected to the amide or carboxylate substituents (see below). Both tolyl groups are almost perpendicular to the pyrrolidine fragments, subtending dihedral angles equal to 84.0 (1) and 75.8 (2)°.
3. Supramolecular features
The title molecule contains seven oxygen atoms suitable for hydrogen bonding. Surprisingly, the only active amino hydrogen atom H11 is not involved in hydrogen bonding. This is the result of β-substituents on pyrrolidine ring atom N1. In the crystal, the hydrogen atoms of the methylene groups C3 and C49 form several short intermolecular C—H⋯O contacts (Table 1, Fig. 2) with the carbonyl oxygen atoms O4, O5 and O7 of an adjacent molecule ( + x, − y, 1 − z) with H⋯O separations of 2.52, 2.58 and 2.63 Å, respectively. A similar absence of hydrogen bonding has been observed in the structures of closely related β-proline trimers and tetramers (Kudryavtsev et al., 2013, 2015a).
by the two bulky4. Database survey
The Cambridge database (version 5.39, Aug 2018; Groom et al., 2016) contains 11 structures of β-proline oligomers. Among these, three are dimeric (CIKHOV, ILOZOY, and ZUYBUS), three are trimeric [CIKHEL and CIKHIP (Kudryavtsev et al., 2013) and OWALEF (Kudryavtsev et al., 2016)] and five are tetrameric (XOQDOY and XOQDUE (Kudryavtsev et al., 2015a), ZUYGUX, ZUYHAE, and ZUYHEI (Kudryavtsev et al., 2015b)]. In total, these structures comprises 25 pyrrolidine fragments. Interestingly, all 25 pyrrolidine rings adopt envelope conformations with the flap carbon atom bearing linking amide –C(=O)N=or terminal –CO2R groups. Endocyclic carbon atoms with aryl substituents and nitrogen atoms always lie in the basal planes of the proline moieties.
5. Synthesis and crystallization
The synthesis and spectroscopic data for the title compound have been reported by Kudryavtsev et al. (2016). The crystal studied was grown by slow evaporation of a methanol solution of the title compound.
6. Refinement
Crystal data, data collection and structure . Aromatic H atoms were placed in calculated positions with C—H = 0.95 Å and refined as riding atoms with Uiso(H) = 1.2Ueq(C). Methyl H atoms were also placed in calculated positions with C—H = 0.98 Å and refined as riding atoms with Uiso(H) = 1.5Ueq(C) and about the C—Me bonds. The amino H atom was found from the difference-Fourier synthesis and refined with both positional and thermal parameters. As the oxygen atoms are the heaviest in the structure, the could not be determined reliably from the diffraction data. The of the pyrrolidine stereogenic centres was assigned on the base of known of the L-menthol precursor (Kudryavtsev et al., 2016).
details are summarized in Table 2Supporting information
CCDC reference: 1905705
https://doi.org/10.1107/S2056989019004079/eb2015sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004079/eb2015Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019004079/eb2015Isup3.cml
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C38H50N2O7 | F(000) = 1392 |
Mr = 646.80 | Dx = 1.244 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2257 reflections |
a = 10.993 (8) Å | θ = 2.4–20.4° |
b = 13.198 (10) Å | µ = 0.09 mm−1 |
c = 23.799 (19) Å | T = 150 K |
V = 3453 (5) Å3 | Needle, colourless |
Z = 4 | 0.50 × 0.10 × 0.04 mm |
Bruker SMART APEXII diffractometer | 3438 independent reflections |
Radiation source: fine-focus sealed tube | 1990 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.169 |
ω scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→13 |
Tmin = 0.959, Tmax = 0.997 | k = −15→15 |
19713 measured reflections | l = −27→28 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0294P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3438 reflections | Δρmax = 0.19 e Å−3 |
436 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0035 (7) |
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. |
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 > 2sigma(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 | 0.3110 (4) | 0.8167 (3) | 0.43708 (16) | 0.0312 (10) | |
N2 | 0.4319 (4) | 1.1224 (3) | 0.4206 (2) | 0.0436 (12) | |
H11 | 0.407 (6) | 1.116 (5) | 0.457 (3) | 0.10 (3)* | |
O1 | 0.1121 (3) | 0.5592 (3) | 0.37321 (14) | 0.0422 (9) | |
O2 | 0.0621 (4) | 0.6760 (3) | 0.30922 (16) | 0.0501 (11) | |
O3 | 0.2308 (3) | 0.7761 (3) | 0.58012 (14) | 0.0464 (10) | |
O4 | 0.3899 (3) | 0.7031 (3) | 0.53704 (15) | 0.0442 (9) | |
O5 | 0.4036 (3) | 0.9273 (2) | 0.49501 (14) | 0.0403 (9) | |
O6 | 0.7399 (3) | 1.1224 (3) | 0.47147 (16) | 0.0510 (10) | |
O7 | 0.5675 (3) | 1.1762 (3) | 0.51165 (17) | 0.0573 (12) | |
C1 | 0.2786 (4) | 0.7736 (4) | 0.3819 (2) | 0.0334 (12) | |
H1 | 0.2707 | 0.8293 | 0.3537 | 0.040* | |
C2 | 0.1512 (4) | 0.7294 (4) | 0.3953 (2) | 0.0349 (13) | |
H2 | 0.0931 | 0.7877 | 0.3943 | 0.042* | |
C3 | 0.1600 (4) | 0.6968 (4) | 0.4560 (2) | 0.0358 (13) | |
H3A | 0.2042 | 0.6318 | 0.4596 | 0.043* | |
H3B | 0.0784 | 0.6897 | 0.4731 | 0.043* | |
C4 | 0.2309 (4) | 0.7833 (4) | 0.48281 (19) | 0.0341 (13) | |
H4 | 0.1733 | 0.8393 | 0.4923 | 0.041* | |
C5 | 0.3734 (4) | 0.6966 (4) | 0.3617 (2) | 0.0325 (12) | |
C6 | 0.3970 (5) | 0.6843 (4) | 0.3047 (2) | 0.0378 (13) | |
C7 | 0.4838 (5) | 0.6134 (4) | 0.2886 (2) | 0.0454 (15) | |
H7 | 0.5010 | 0.6046 | 0.2498 | 0.054* | |
C8 | 0.5454 (5) | 0.5555 (5) | 0.3274 (2) | 0.0482 (15) | |
H8 | 0.6047 | 0.5078 | 0.3154 | 0.058* | |
C9 | 0.5203 (5) | 0.5676 (4) | 0.3839 (2) | 0.0469 (15) | |
H9 | 0.5608 | 0.5272 | 0.4111 | 0.056* | |
C10 | 0.4355 (4) | 0.6392 (4) | 0.4004 (2) | 0.0393 (13) | |
H10 | 0.4199 | 0.6488 | 0.4393 | 0.047* | |
C11 | 0.1050 (5) | 0.6535 (4) | 0.3537 (2) | 0.0347 (13) | |
C12 | 0.2549 (5) | 0.4131 (4) | 0.3088 (2) | 0.0519 (16) | |
H12 | 0.2946 | 0.4681 | 0.3312 | 0.062* | |
C13 | 0.3418 (6) | 0.3231 (5) | 0.3088 (3) | 0.074 (2) | |
H13A | 0.3423 | 0.2917 | 0.3461 | 0.111* | |
H13B | 0.4240 | 0.3464 | 0.2995 | 0.111* | |
H13C | 0.3150 | 0.2734 | 0.2809 | 0.111* | |
C14 | 0.2384 (6) | 0.4538 (5) | 0.2488 (2) | 0.0645 (18) | |
H14A | 0.3182 | 0.4697 | 0.2327 | 0.097* | |
H14B | 0.1886 | 0.5154 | 0.2498 | 0.097* | |
H14C | 0.1981 | 0.4024 | 0.2257 | 0.097* | |
C15 | −0.2423 (5) | 0.3419 (4) | 0.3906 (3) | 0.0611 (18) | |
H15A | −0.2895 | 0.2858 | 0.3748 | 0.092* | |
H15B | −0.2943 | 0.4019 | 0.3940 | 0.092* | |
H15C | −0.2118 | 0.3227 | 0.4278 | 0.092* | |
C16 | 0.2962 (5) | 0.7515 (4) | 0.5349 (2) | 0.0357 (13) | |
C17 | 0.2759 (5) | 0.7423 (5) | 0.6340 (2) | 0.0579 (17) | |
H17A | 0.2106 | 0.7463 | 0.6619 | 0.087* | |
H17B | 0.3437 | 0.7857 | 0.6457 | 0.087* | |
H17C | 0.3041 | 0.6721 | 0.6310 | 0.087* | |
C18 | 0.3889 (5) | 0.8945 (4) | 0.4471 (2) | 0.0334 (12) | |
C19 | 0.3782 (4) | 1.0456 (4) | 0.3845 (2) | 0.0376 (13) | |
H19 | 0.3982 | 1.0647 | 0.3449 | 0.045* | |
C20 | 0.4485 (4) | 0.9445 (4) | 0.3976 (2) | 0.0378 (13) | |
H20 | 0.4506 | 0.8986 | 0.3642 | 0.045* | |
C21 | 0.5763 (4) | 0.9835 (4) | 0.4127 (2) | 0.0437 (15) | |
H21A | 0.6346 | 0.9690 | 0.3820 | 0.052* | |
H21B | 0.6060 | 0.9513 | 0.4476 | 0.052* | |
C22 | 0.5611 (5) | 1.0986 (4) | 0.4208 (2) | 0.0412 (14) | |
H22 | 0.5995 | 1.1335 | 0.3880 | 0.049* | |
C23 | 0.6197 (5) | 1.1381 (4) | 0.4736 (3) | 0.0430 (14) | |
C24 | 0.8099 (5) | 1.1593 (5) | 0.5196 (3) | 0.0618 (18) | |
H24A | 0.8920 | 1.1779 | 0.5073 | 0.093* | |
H24B | 0.8152 | 1.1059 | 0.5481 | 0.093* | |
H24C | 0.7695 | 1.2188 | 0.5356 | 0.093* | |
C25 | 0.2412 (4) | 1.0401 (3) | 0.3886 (2) | 0.0349 (13) | |
C26 | 0.1694 (5) | 1.0283 (4) | 0.3403 (2) | 0.0381 (13) | |
C27 | 0.0444 (5) | 1.0164 (4) | 0.3473 (3) | 0.0551 (17) | |
H27 | −0.0051 | 1.0071 | 0.3150 | 0.066* | |
C28 | −0.0096 (6) | 1.0178 (4) | 0.3992 (4) | 0.066 (2) | |
H28 | −0.0951 | 1.0091 | 0.4025 | 0.080* | |
C29 | 0.0595 (6) | 1.0314 (5) | 0.4460 (3) | 0.0619 (19) | |
H29 | 0.0223 | 1.0322 | 0.4821 | 0.074* | |
C30 | 0.1839 (5) | 1.0443 (4) | 0.4410 (2) | 0.0478 (15) | |
H30 | 0.2313 | 1.0562 | 0.4738 | 0.057* | |
C31 | 0.2218 (5) | 1.0293 (4) | 0.2826 (2) | 0.0540 (17) | |
H31A | 0.1569 | 1.0182 | 0.2551 | 0.081* | |
H31B | 0.2827 | 0.9754 | 0.2792 | 0.081* | |
H31C | 0.2604 | 1.0951 | 0.2755 | 0.081* | |
C32 | 0.3347 (5) | 0.7466 (4) | 0.2601 (2) | 0.0518 (16) | |
H32A | 0.2468 | 0.7472 | 0.2671 | 0.078* | |
H32B | 0.3509 | 0.7170 | 0.2231 | 0.078* | |
H32C | 0.3659 | 0.8161 | 0.2612 | 0.078* | |
C44 | 0.0484 (5) | 0.4778 (4) | 0.3427 (2) | 0.0407 (14) | |
H44A | 0.0258 | 0.5020 | 0.3043 | 0.049* | |
C45 | 0.1339 (5) | 0.3885 (4) | 0.3380 (2) | 0.0451 (14) | |
H45 | 0.1538 | 0.3664 | 0.3771 | 0.054* | |
C46 | 0.0616 (5) | 0.3019 (4) | 0.3104 (2) | 0.0557 (17) | |
H46A | 0.0371 | 0.3220 | 0.2720 | 0.067* | |
H46B | 0.1137 | 0.2409 | 0.3075 | 0.067* | |
C47 | −0.0515 (5) | 0.2770 (4) | 0.3450 (3) | 0.0550 (16) | |
H47A | −0.0964 | 0.2213 | 0.3264 | 0.066* | |
H47B | −0.0260 | 0.2528 | 0.3825 | 0.066* | |
C48 | −0.1351 (5) | 0.3657 (4) | 0.3520 (2) | 0.0468 (15) | |
H48 | −0.1676 | 0.3849 | 0.3142 | 0.056* | |
C49 | −0.0645 (5) | 0.4561 (4) | 0.3758 (2) | 0.0426 (14) | |
H49C | −0.1175 | 0.5168 | 0.3755 | 0.051* | |
H49A | −0.0421 | 0.4418 | 0.4153 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.032 (2) | 0.026 (3) | 0.035 (2) | −0.003 (2) | 0.002 (2) | 0.0005 (19) |
N2 | 0.036 (3) | 0.038 (3) | 0.056 (3) | −0.003 (2) | −0.008 (3) | −0.002 (3) |
O1 | 0.050 (2) | 0.028 (2) | 0.048 (2) | −0.0019 (18) | −0.012 (2) | −0.0016 (17) |
O2 | 0.064 (3) | 0.035 (2) | 0.051 (2) | −0.006 (2) | −0.018 (2) | 0.0069 (19) |
O3 | 0.044 (2) | 0.060 (3) | 0.036 (2) | 0.0077 (19) | 0.006 (2) | 0.0026 (18) |
O4 | 0.042 (2) | 0.040 (2) | 0.050 (2) | 0.0087 (19) | −0.005 (2) | 0.0033 (17) |
O5 | 0.047 (2) | 0.033 (2) | 0.041 (2) | −0.0036 (17) | 0.002 (2) | −0.0061 (17) |
O6 | 0.044 (2) | 0.051 (3) | 0.058 (3) | −0.0057 (19) | −0.005 (2) | −0.011 (2) |
O7 | 0.045 (3) | 0.068 (3) | 0.059 (3) | −0.001 (2) | 0.002 (2) | −0.018 (2) |
C1 | 0.032 (3) | 0.033 (3) | 0.036 (3) | −0.006 (2) | 0.001 (3) | −0.002 (2) |
C2 | 0.031 (3) | 0.035 (3) | 0.039 (3) | 0.004 (2) | −0.001 (3) | 0.000 (3) |
C3 | 0.029 (3) | 0.036 (3) | 0.043 (3) | −0.005 (2) | 0.002 (3) | 0.001 (3) |
C4 | 0.026 (3) | 0.036 (3) | 0.040 (3) | 0.002 (2) | 0.001 (3) | −0.002 (2) |
C5 | 0.031 (3) | 0.030 (3) | 0.036 (3) | −0.005 (2) | 0.001 (3) | 0.000 (2) |
C6 | 0.034 (3) | 0.041 (4) | 0.039 (3) | −0.007 (3) | 0.000 (3) | 0.001 (3) |
C7 | 0.040 (3) | 0.054 (4) | 0.042 (3) | 0.004 (3) | 0.009 (3) | −0.004 (3) |
C8 | 0.037 (3) | 0.053 (4) | 0.055 (4) | 0.009 (3) | 0.001 (3) | −0.010 (3) |
C9 | 0.039 (3) | 0.047 (4) | 0.055 (4) | 0.007 (3) | −0.003 (3) | −0.001 (3) |
C10 | 0.028 (3) | 0.044 (4) | 0.045 (3) | 0.002 (3) | −0.004 (3) | −0.006 (3) |
C11 | 0.024 (3) | 0.031 (4) | 0.049 (3) | 0.003 (2) | 0.003 (3) | 0.006 (3) |
C12 | 0.055 (4) | 0.049 (4) | 0.052 (4) | 0.004 (3) | 0.005 (3) | −0.014 (3) |
C13 | 0.069 (5) | 0.056 (5) | 0.097 (5) | 0.013 (4) | 0.018 (4) | −0.013 (4) |
C14 | 0.063 (4) | 0.079 (5) | 0.052 (4) | −0.006 (4) | 0.009 (4) | −0.013 (3) |
C15 | 0.062 (4) | 0.045 (4) | 0.076 (4) | −0.012 (3) | −0.008 (4) | 0.008 (3) |
C16 | 0.033 (3) | 0.034 (3) | 0.041 (3) | −0.004 (3) | 0.003 (3) | 0.006 (3) |
C17 | 0.061 (4) | 0.079 (5) | 0.034 (3) | 0.007 (3) | 0.000 (3) | 0.005 (3) |
C18 | 0.031 (3) | 0.029 (3) | 0.040 (3) | 0.004 (3) | 0.001 (3) | −0.001 (3) |
C19 | 0.038 (3) | 0.036 (4) | 0.039 (3) | 0.001 (3) | −0.001 (3) | 0.002 (3) |
C20 | 0.034 (3) | 0.033 (3) | 0.047 (3) | −0.002 (2) | 0.009 (3) | −0.010 (3) |
C21 | 0.035 (3) | 0.040 (4) | 0.056 (4) | −0.010 (2) | 0.006 (3) | −0.008 (3) |
C22 | 0.045 (3) | 0.031 (4) | 0.047 (3) | −0.014 (3) | 0.001 (3) | 0.001 (3) |
C23 | 0.036 (3) | 0.036 (4) | 0.057 (4) | −0.004 (3) | 0.002 (3) | −0.002 (3) |
C24 | 0.043 (4) | 0.076 (5) | 0.066 (4) | 0.000 (3) | −0.007 (4) | −0.019 (3) |
C25 | 0.035 (3) | 0.022 (3) | 0.048 (3) | 0.002 (2) | 0.004 (3) | 0.003 (2) |
C26 | 0.031 (3) | 0.028 (3) | 0.055 (4) | −0.001 (2) | −0.001 (3) | 0.001 (3) |
C27 | 0.040 (4) | 0.042 (4) | 0.084 (5) | 0.001 (3) | −0.002 (4) | −0.002 (3) |
C28 | 0.033 (4) | 0.042 (4) | 0.124 (7) | 0.007 (3) | 0.015 (5) | 0.019 (4) |
C29 | 0.048 (4) | 0.055 (5) | 0.083 (5) | 0.021 (3) | 0.018 (4) | 0.019 (4) |
C30 | 0.047 (4) | 0.040 (4) | 0.056 (4) | 0.012 (3) | 0.007 (3) | 0.010 (3) |
C31 | 0.050 (4) | 0.052 (4) | 0.060 (4) | 0.005 (3) | −0.011 (3) | −0.016 (3) |
C32 | 0.054 (4) | 0.053 (4) | 0.048 (3) | 0.009 (3) | 0.009 (3) | 0.002 (3) |
C44 | 0.049 (4) | 0.028 (3) | 0.044 (3) | −0.004 (3) | −0.011 (3) | −0.005 (3) |
C45 | 0.044 (3) | 0.040 (4) | 0.051 (3) | 0.003 (3) | −0.004 (3) | −0.007 (3) |
C46 | 0.063 (4) | 0.038 (4) | 0.066 (4) | −0.002 (3) | 0.000 (4) | −0.013 (3) |
C47 | 0.066 (4) | 0.034 (4) | 0.065 (4) | −0.011 (3) | −0.015 (4) | −0.004 (3) |
C48 | 0.044 (4) | 0.038 (4) | 0.058 (4) | −0.003 (3) | −0.010 (3) | 0.010 (3) |
C49 | 0.048 (3) | 0.030 (3) | 0.050 (3) | 0.002 (3) | −0.006 (3) | 0.005 (3) |
N1—C18 | 1.357 (6) | C15—H15C | 0.9800 |
N1—C4 | 1.468 (6) | C17—H17A | 0.9800 |
N1—C1 | 1.475 (6) | C17—H17B | 0.9800 |
N2—C19 | 1.453 (6) | C17—H17C | 0.9800 |
N2—C22 | 1.455 (7) | C18—C20 | 1.501 (7) |
N2—H11 | 0.91 (6) | C19—C25 | 1.511 (7) |
O1—C11 | 1.331 (6) | C19—C20 | 1.573 (7) |
O1—C44 | 1.473 (6) | C19—H19 | 1.0000 |
O2—C11 | 1.196 (6) | C20—C21 | 1.538 (7) |
O3—C16 | 1.333 (6) | C20—H20 | 1.0000 |
O3—C17 | 1.446 (6) | C21—C22 | 1.540 (7) |
O4—C16 | 1.213 (6) | C21—H21A | 0.9900 |
O5—C18 | 1.231 (5) | C21—H21B | 0.9900 |
O6—C23 | 1.339 (6) | C22—C23 | 1.505 (7) |
O6—C24 | 1.464 (6) | C22—H22 | 1.0000 |
O7—C23 | 1.185 (6) | C24—H24A | 0.9800 |
C1—C5 | 1.533 (7) | C24—H24B | 0.9800 |
C1—C2 | 1.550 (6) | C24—H24C | 0.9800 |
C1—H1 | 1.0000 | C25—C30 | 1.399 (7) |
C2—C11 | 1.497 (7) | C25—C26 | 1.403 (7) |
C2—C3 | 1.511 (7) | C26—C27 | 1.393 (7) |
C2—H2 | 1.0000 | C26—C31 | 1.489 (8) |
C3—C4 | 1.523 (7) | C27—C28 | 1.370 (9) |
C3—H3A | 0.9900 | C27—H27 | 0.9500 |
C3—H3B | 0.9900 | C28—C29 | 1.360 (9) |
C4—C16 | 1.493 (7) | C28—H28 | 0.9500 |
C4—H4 | 1.0000 | C29—C30 | 1.384 (8) |
C5—C10 | 1.376 (7) | C29—H29 | 0.9500 |
C5—C6 | 1.389 (6) | C30—H30 | 0.9500 |
C6—C7 | 1.391 (7) | C31—H31A | 0.9800 |
C6—C32 | 1.507 (7) | C31—H31B | 0.9800 |
C7—C8 | 1.376 (7) | C31—H31C | 0.9800 |
C7—H7 | 0.9500 | C32—H32A | 0.9800 |
C8—C9 | 1.382 (7) | C32—H32B | 0.9800 |
C8—H8 | 0.9500 | C32—H32C | 0.9800 |
C9—C10 | 1.384 (7) | C44—C49 | 1.498 (7) |
C9—H9 | 0.9500 | C44—C45 | 1.512 (7) |
C10—H10 | 0.9500 | C44—H44A | 1.0000 |
C12—C13 | 1.524 (8) | C45—C46 | 1.539 (7) |
C12—C45 | 1.536 (7) | C45—H45 | 1.0000 |
C12—C14 | 1.537 (7) | C46—C47 | 1.525 (7) |
C12—H12 | 1.0000 | C46—H46A | 0.9900 |
C13—H13A | 0.9800 | C46—H46B | 0.9900 |
C13—H13B | 0.9800 | C47—C48 | 1.498 (8) |
C13—H13C | 0.9800 | C47—H47A | 0.9900 |
C14—H14A | 0.9800 | C47—H47B | 0.9900 |
C14—H14B | 0.9800 | C48—C49 | 1.532 (7) |
C14—H14C | 0.9800 | C48—H48 | 1.0000 |
C15—C48 | 1.527 (7) | C49—H49C | 0.9900 |
C15—H15A | 0.9800 | C49—H49A | 0.9900 |
C15—H15B | 0.9800 | ||
C18—N1—C4 | 118.4 (4) | C20—C19—H19 | 107.0 |
C18—N1—C1 | 126.9 (4) | C18—C20—C21 | 111.3 (5) |
C4—N1—C1 | 113.5 (4) | C18—C20—C19 | 108.3 (4) |
C19—N2—C22 | 104.4 (4) | C21—C20—C19 | 102.2 (4) |
C19—N2—H11 | 112 (4) | C18—C20—H20 | 111.6 |
C22—N2—H11 | 106 (4) | C21—C20—H20 | 111.6 |
C11—O1—C44 | 118.8 (4) | C19—C20—H20 | 111.6 |
C16—O3—C17 | 117.1 (4) | C20—C21—C22 | 105.1 (4) |
C23—O6—C24 | 116.0 (5) | C20—C21—H21A | 110.7 |
N1—C1—C5 | 111.8 (4) | C22—C21—H21A | 110.7 |
N1—C1—C2 | 100.4 (4) | C20—C21—H21B | 110.7 |
C5—C1—C2 | 115.4 (4) | C22—C21—H21B | 110.7 |
N1—C1—H1 | 109.6 | H21A—C21—H21B | 108.8 |
C5—C1—H1 | 109.6 | N2—C22—C23 | 110.2 (5) |
C2—C1—H1 | 109.6 | N2—C22—C21 | 108.5 (4) |
C11—C2—C3 | 117.6 (4) | C23—C22—C21 | 113.6 (5) |
C11—C2—C1 | 115.0 (4) | N2—C22—H22 | 108.1 |
C3—C2—C1 | 104.2 (4) | C23—C22—H22 | 108.1 |
C11—C2—H2 | 106.4 | C21—C22—H22 | 108.1 |
C3—C2—H2 | 106.4 | O7—C23—O6 | 124.9 (5) |
C1—C2—H2 | 106.4 | O7—C23—C22 | 125.3 (5) |
C2—C3—C4 | 102.7 (4) | O6—C23—C22 | 109.7 (5) |
C2—C3—H3A | 111.2 | O6—C24—H24A | 109.5 |
C4—C3—H3A | 111.2 | O6—C24—H24B | 109.5 |
C2—C3—H3B | 111.2 | H24A—C24—H24B | 109.5 |
C4—C3—H3B | 111.2 | O6—C24—H24C | 109.5 |
H3A—C3—H3B | 109.1 | H24A—C24—H24C | 109.5 |
N1—C4—C16 | 114.4 (4) | H24B—C24—H24C | 109.5 |
N1—C4—C3 | 102.8 (4) | C30—C25—C26 | 118.8 (5) |
C16—C4—C3 | 112.6 (4) | C30—C25—C19 | 120.3 (5) |
N1—C4—H4 | 109.0 | C26—C25—C19 | 120.9 (5) |
C16—C4—H4 | 109.0 | C27—C26—C25 | 118.0 (6) |
C3—C4—H4 | 109.0 | C27—C26—C31 | 119.6 (6) |
C10—C5—C6 | 119.8 (5) | C25—C26—C31 | 122.5 (5) |
C10—C5—C1 | 119.4 (4) | C28—C27—C26 | 122.3 (6) |
C6—C5—C1 | 120.7 (5) | C28—C27—H27 | 118.9 |
C5—C6—C7 | 118.4 (5) | C26—C27—H27 | 118.9 |
C5—C6—C32 | 122.6 (5) | C29—C28—C27 | 119.9 (6) |
C7—C6—C32 | 119.0 (5) | C29—C28—H28 | 120.0 |
C8—C7—C6 | 121.8 (5) | C27—C28—H28 | 120.0 |
C8—C7—H7 | 119.1 | C28—C29—C30 | 119.8 (7) |
C6—C7—H7 | 119.1 | C28—C29—H29 | 120.1 |
C7—C8—C9 | 119.4 (5) | C30—C29—H29 | 120.1 |
C7—C8—H8 | 120.3 | C29—C30—C25 | 121.1 (6) |
C9—C8—H8 | 120.3 | C29—C30—H30 | 119.4 |
C8—C9—C10 | 119.3 (5) | C25—C30—H30 | 119.4 |
C8—C9—H9 | 120.3 | C26—C31—H31A | 109.5 |
C10—C9—H9 | 120.3 | C26—C31—H31B | 109.5 |
C5—C10—C9 | 121.3 (5) | H31A—C31—H31B | 109.5 |
C5—C10—H10 | 119.4 | C26—C31—H31C | 109.5 |
C9—C10—H10 | 119.4 | H31A—C31—H31C | 109.5 |
O2—C11—O1 | 124.3 (5) | H31B—C31—H31C | 109.5 |
O2—C11—C2 | 123.6 (5) | C6—C32—H32A | 109.5 |
O1—C11—C2 | 112.0 (5) | C6—C32—H32B | 109.5 |
C13—C12—C45 | 112.2 (5) | H32A—C32—H32B | 109.5 |
C13—C12—C14 | 110.3 (5) | C6—C32—H32C | 109.5 |
C45—C12—C14 | 113.1 (5) | H32A—C32—H32C | 109.5 |
C13—C12—H12 | 107.0 | H32B—C32—H32C | 109.5 |
C45—C12—H12 | 107.0 | O1—C44—C49 | 105.9 (4) |
C14—C12—H12 | 107.0 | O1—C44—C45 | 108.1 (4) |
C12—C13—H13A | 109.5 | C49—C44—C45 | 113.9 (4) |
C12—C13—H13B | 109.5 | O1—C44—H44A | 109.6 |
H13A—C13—H13B | 109.5 | C49—C44—H44A | 109.6 |
C12—C13—H13C | 109.5 | C45—C44—H44A | 109.6 |
H13A—C13—H13C | 109.5 | C44—C45—C12 | 114.0 (5) |
H13B—C13—H13C | 109.5 | C44—C45—C46 | 106.9 (4) |
C12—C14—H14A | 109.5 | C12—C45—C46 | 114.3 (5) |
C12—C14—H14B | 109.5 | C44—C45—H45 | 107.1 |
H14A—C14—H14B | 109.5 | C12—C45—H45 | 107.1 |
C12—C14—H14C | 109.5 | C46—C45—H45 | 107.1 |
H14A—C14—H14C | 109.5 | C47—C46—C45 | 110.5 (5) |
H14B—C14—H14C | 109.5 | C47—C46—H46A | 109.5 |
C48—C15—H15A | 109.5 | C45—C46—H46A | 109.5 |
C48—C15—H15B | 109.5 | C47—C46—H46B | 109.5 |
H15A—C15—H15B | 109.5 | C45—C46—H46B | 109.5 |
C48—C15—H15C | 109.5 | H46A—C46—H46B | 108.1 |
H15A—C15—H15C | 109.5 | C48—C47—C46 | 113.1 (5) |
H15B—C15—H15C | 109.5 | C48—C47—H47A | 109.0 |
O4—C16—O3 | 123.5 (5) | C46—C47—H47A | 109.0 |
O4—C16—C4 | 126.2 (5) | C48—C47—H47B | 109.0 |
O3—C16—C4 | 110.1 (4) | C46—C47—H47B | 109.0 |
O3—C17—H17A | 109.5 | H47A—C47—H47B | 107.8 |
O3—C17—H17B | 109.5 | C47—C48—C15 | 112.3 (5) |
H17A—C17—H17B | 109.5 | C47—C48—C49 | 109.8 (4) |
O3—C17—H17C | 109.5 | C15—C48—C49 | 109.2 (5) |
H17A—C17—H17C | 109.5 | C47—C48—H48 | 108.5 |
H17B—C17—H17C | 109.5 | C15—C48—H48 | 108.5 |
O5—C18—N1 | 120.7 (5) | C49—C48—H48 | 108.5 |
O5—C18—C20 | 121.0 (5) | C44—C49—C48 | 112.0 (4) |
N1—C18—C20 | 118.1 (4) | C44—C49—H49C | 109.2 |
N2—C19—C25 | 113.6 (4) | C48—C49—H49C | 109.2 |
N2—C19—C20 | 106.0 (4) | C44—C49—H49A | 109.2 |
C25—C19—C20 | 115.9 (4) | C48—C49—H49A | 109.2 |
N2—C19—H19 | 107.0 | H49C—C49—H49A | 107.9 |
C25—C19—H19 | 107.0 | ||
C18—N1—C1—C5 | 82.6 (6) | N1—C18—C20—C19 | 100.2 (5) |
C4—N1—C1—C5 | −110.1 (4) | N2—C19—C20—C18 | 85.9 (5) |
C18—N1—C1—C2 | −154.5 (4) | C25—C19—C20—C18 | −41.1 (6) |
C4—N1—C1—C2 | 12.8 (5) | N2—C19—C20—C21 | −31.7 (5) |
N1—C1—C2—C11 | −163.0 (4) | C25—C19—C20—C21 | −158.6 (5) |
C5—C1—C2—C11 | −42.6 (6) | C18—C20—C21—C22 | −102.5 (5) |
N1—C1—C2—C3 | −32.9 (5) | C19—C20—C21—C22 | 12.9 (5) |
C5—C1—C2—C3 | 87.5 (5) | C19—N2—C22—C23 | −154.8 (4) |
C11—C2—C3—C4 | 169.7 (4) | C19—N2—C22—C21 | −29.9 (6) |
C1—C2—C3—C4 | 41.1 (5) | C20—C21—C22—N2 | 9.5 (6) |
C18—N1—C4—C16 | −57.3 (6) | C20—C21—C22—C23 | 132.5 (5) |
C1—N1—C4—C16 | 134.2 (4) | C24—O6—C23—O7 | −2.5 (8) |
C18—N1—C4—C3 | −179.7 (4) | C24—O6—C23—C22 | 178.5 (4) |
C1—N1—C4—C3 | 11.9 (5) | N2—C22—C23—O7 | 5.4 (8) |
C2—C3—C4—N1 | −32.2 (5) | C21—C22—C23—O7 | −116.6 (6) |
C2—C3—C4—C16 | −155.7 (4) | N2—C22—C23—O6 | −175.6 (4) |
N1—C1—C5—C10 | 31.8 (6) | C21—C22—C23—O6 | 62.4 (6) |
C2—C1—C5—C10 | −82.1 (6) | N2—C19—C25—C30 | −43.5 (6) |
N1—C1—C5—C6 | −148.2 (4) | C20—C19—C25—C30 | 79.5 (6) |
C2—C1—C5—C6 | 97.8 (6) | N2—C19—C25—C26 | 138.0 (5) |
C10—C5—C6—C7 | 0.0 (8) | C20—C19—C25—C26 | −99.0 (6) |
C1—C5—C6—C7 | −179.9 (5) | C30—C25—C26—C27 | −3.1 (7) |
C10—C5—C6—C32 | −178.4 (5) | C19—C25—C26—C27 | 175.4 (5) |
C1—C5—C6—C32 | 1.7 (8) | C30—C25—C26—C31 | 176.2 (5) |
C5—C6—C7—C8 | 0.4 (8) | C19—C25—C26—C31 | −5.3 (7) |
C32—C6—C7—C8 | 178.8 (5) | C25—C26—C27—C28 | 1.2 (8) |
C6—C7—C8—C9 | 0.3 (9) | C31—C26—C27—C28 | −178.1 (5) |
C7—C8—C9—C10 | −1.4 (9) | C26—C27—C28—C29 | 0.3 (9) |
C6—C5—C10—C9 | −1.1 (8) | C27—C28—C29—C30 | 0.2 (9) |
C1—C5—C10—C9 | 178.9 (4) | C28—C29—C30—C25 | −2.2 (9) |
C8—C9—C10—C5 | 1.8 (8) | C26—C25—C30—C29 | 3.6 (7) |
C44—O1—C11—O2 | −9.1 (7) | C19—C25—C30—C29 | −174.9 (5) |
C44—O1—C11—C2 | 167.9 (4) | C11—O1—C44—C49 | −102.4 (5) |
C3—C2—C11—O2 | 158.3 (5) | C11—O1—C44—C45 | 135.1 (5) |
C1—C2—C11—O2 | −78.4 (6) | O1—C44—C45—C12 | −57.3 (6) |
C3—C2—C11—O1 | −18.7 (6) | C49—C44—C45—C12 | −174.7 (4) |
C1—C2—C11—O1 | 104.6 (5) | O1—C44—C45—C46 | 175.4 (4) |
C17—O3—C16—O4 | −0.1 (7) | C49—C44—C45—C46 | 58.0 (6) |
C17—O3—C16—C4 | 174.5 (4) | C13—C12—C45—C44 | 175.8 (5) |
N1—C4—C16—O4 | −39.9 (7) | C14—C12—C45—C44 | −58.7 (6) |
C3—C4—C16—O4 | 76.9 (6) | C13—C12—C45—C46 | −60.9 (6) |
N1—C4—C16—O3 | 145.6 (4) | C14—C12—C45—C46 | 64.6 (6) |
C3—C4—C16—O3 | −97.5 (5) | C44—C45—C46—C47 | −57.6 (6) |
C4—N1—C18—O5 | 9.4 (7) | C12—C45—C46—C47 | 175.3 (5) |
C1—N1—C18—O5 | 176.1 (5) | C45—C46—C47—C48 | 58.6 (6) |
C4—N1—C18—C20 | −165.7 (4) | C46—C47—C48—C15 | −175.3 (4) |
C1—N1—C18—C20 | 1.0 (7) | C46—C47—C48—C49 | −53.6 (6) |
C22—N2—C19—C25 | 166.6 (4) | O1—C44—C49—C48 | −174.8 (4) |
C22—N2—C19—C20 | 38.2 (5) | C45—C44—C49—C48 | −56.2 (6) |
O5—C18—C20—C21 | 36.7 (7) | C47—C48—C49—C44 | 51.4 (6) |
N1—C18—C20—C21 | −148.3 (4) | C15—C48—C49—C44 | 174.9 (4) |
O5—C18—C20—C19 | −74.8 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O4i | 0.99 | 2.52 | 3.254 (6) | 131 |
C3—H3B···O5i | 0.99 | 2.58 | 3.462 (6) | 149 |
C49—H49A···O7i | 0.99 | 2.63 | 3.511 (7) | 149 |
Symmetry code: (i) x−1/2, −y+3/2, −z+1. |
Funding information
PMI was supported by a scholarship of the President of the Russian Federation (grant No. SP-1278.2018.4). MNS was supported by the Russian Foundation for Basic Research (grant No. 18–33-01260 mol_a). X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS.
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