organic compounds
[1–9-NαC]-Linusorb B3 (cyclolinopeptide A) acetonitrile disolvate
aDepartment of Plant Sciences, College of Agriculture and Bioresources, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5A8, Canada, bSaskatchewan Structural Sciences Centre, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan S7N 5C9, Canada, and cGuangdong Saskatchewan Oilseed Joint Laboratory, Department of Food Science and Engineering, Jinan University, Guangzhou, Guangdong 510632, People's Republic of China
*Correspondence e-mail: martin.reaney@usask.ca
The title compound, C57H85N9O9·2C2H3N [systematic name: cyclo-(prolyl-prolyl-phenylalanyl-phenylalanyl-leucyl-isoleucyl-isoleucylleucyl-valyl) acetonitrile disolvate; synonym: cyclolinopeptide acetonitrile disolvate], is a polypeptide with nine amino acids, viz. NαC-(Pro1–Pro2–Phe3–Phe4–Leu5–Ile6–Ile7–Leu8–Val9). It was extracted from flaxseed oil and crystallized from acetonitrile as a disolvate. In the title molecule, there are four intramolecular N—H⋯O hydrogen bonds. One of the two acetonitrile molecules is hydrogen bonded to Phe3 via an N—H⋯N hydrogen bond, while the second acetonitrile molecule is located at the other side of the peptide ring and is linked to the title molecule by a C—H⋯N hydrogen bond. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains along the a-axis direction. The chains are linked by C—H⋯O hydrogen bonds, forming undulating layers parallel to the ac plane.
Keywords: crystal structure; cyclic peptide; orbitides; cyclolinopeptide A; [1–9-NαC]-linusorb B3; acetonitrile; hydrogen bonding.
CCDC reference: 1511350
Structure description
Several cyclic Linum usitatissimum L). The isolation and purification procedures used have been reported (Kaufmann & Tobschirbel, 1959; Reaney et al., 2013), as have the amino acid composition and sequencing methods (Prox & Weygand, 1966). Different solvents have been used to grow crystals of the title compound, and the crystal structures of a number of polymorphs have been reported. For example, different orthorhombic polymorphs have been obtained from chloroform (Huben et al., 2014), methanol (Quail et al., 2009), methanol/2-propanol (Matsumoto et al., 2002), water/2-2-propanol (Di Blasio et al., 1987, 1989) and benzene/acetonitrile (Saviano et al., 1995). The last polymorph crystallized as an acetonitrile monosolvate monohydrate. It has been shown that the title compound tends to self-assemble, under suitable conditions, from zero-dimensional objects to one-dimensional nanofibers and finally producing a three-dimensional supramolecular gel network (Rogers et al., 2016).
have been isolated from flaxseed (A systematic naming system specifically for the Type VI cyclic et al., 2015). Hence the name of the title compound [1–9-NαC]-linusorb B3 (cyclolinopeptide A). Herein, we report on the of a new orthorhombic polymorph of the title compound that crystallized as an acteonitrile disolvate.
such as the title compound, that `reflects the taxonomic name of the species producing the orbitides and a numbering system that enables systematic representation of amino acid residues and modifications' has been proposed by our group (ShimThe molecular structure of the title [1–9-NαC]-linusorb B3 molecule is illustrated in Fig. 1. The peptide backbone ring is twisted to form four intramolecular hydrogen bonds between the amino acids (N4—H4N⋯O9, N9—H9N⋯O4, N8—H8⋯O5 and N7—H7⋯O5), as shown in Fig. 1 and Table 1.
In the crystal, one of the two acetonitrile molecules is hydrogen bonded to phe3 via an N3—H3⋯N1S hydrogen bond (Table 1 and Fig. 2). The second acetonitrile molecule is located at the other side of the peptide ring and the C≡N bond is positioned proximate to a CHx-rich environment, and is linked to the title molecule by a C—H⋯N hydrogen bond. The [1–9-NαC]-linusorb B3 molecules are linked in chains along the a-axis direction by two intermolecular hydrogen bonds, namely N5—H5⋯O8i and N6—H6⋯O8i (Table 1), as shown in Fig. 2. The chains are linked via C—H⋯O hydrogen bonds, forming undulating layers parallel to the ac plane (Fig. 3).
Synthesis and crystallization
Suitable crystals of the title compound were isolated from a solution of [1–9-NαC]-linusorb B3 in acetonitrile when the solvent was allowed to evaporate slowly at ambient temperature.
Refinement
Crystal data, data collection and structure . The reflections 140, 038, 060, 119, 108, 19, 77 and 360 were affected by the beam-stop and were omitted from the final refinement.
details are summarized in Table 2
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Structural data
CCDC reference: 1511350
https://doi.org/10.1107/S2414314616017065/su4085sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017065/su4085Isup2.hkl
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXTL (Sheldrick 2008).C57H85N9O9·2C2H3N | Dx = 1.170 Mg m−3 |
Mr = 1122.44 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 9122 reflections |
a = 9.6524 (6) Å | θ = 2.5–68.3° |
b = 22.6947 (13) Å | µ = 0.64 mm−1 |
c = 29.0945 (17) Å | T = 100 K |
V = 6373.4 (7) Å3 | Rod, colourless |
Z = 4 | 0.55 × 0.06 × 0.06 mm |
F(000) = 2424 |
Bruker APEXII CCD diffractometer | 9085 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.086 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | θmax = 68.4°, θmin = 2.5° |
Tmin = 0.587, Tmax = 0.753 | h = −11→6 |
47444 measured reflections | k = −26→27 |
11348 independent reflections | l = −33→34 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.166 | w = 1/[σ2(Fo2) + (0.0949P)2 + 1.8264P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
11348 reflections | Δρmax = 0.29 e Å−3 |
742 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 3356 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.16 (11) |
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 | 0.9530 (4) | 0.69914 (15) | 0.15822 (12) | 0.0353 (8) | |
O2 | 0.4072 (4) | 0.75979 (15) | 0.21331 (12) | 0.0371 (8) | |
O3 | 0.2530 (4) | 0.58487 (16) | 0.22979 (12) | 0.0350 (8) | |
O4 | 0.6377 (3) | 0.55765 (14) | 0.34502 (10) | 0.0259 (7) | |
O5 | 0.5884 (3) | 0.64306 (13) | 0.45172 (11) | 0.0270 (7) | |
O6 | 0.5764 (4) | 0.51419 (15) | 0.52030 (11) | 0.0321 (8) | |
O7 | 1.0051 (3) | 0.50867 (14) | 0.42400 (11) | 0.0297 (8) | |
O8 | 1.1564 (4) | 0.61766 (15) | 0.36511 (11) | 0.0311 (8) | |
O9 | 0.7741 (4) | 0.60902 (15) | 0.24898 (12) | 0.0329 (8) | |
N1 | 0.9425 (4) | 0.67747 (17) | 0.25304 (14) | 0.0278 (9) | |
N2 | 0.7444 (4) | 0.74399 (17) | 0.15876 (14) | 0.0290 (9) | |
N3 | 0.5053 (4) | 0.68133 (16) | 0.17730 (13) | 0.0254 (9) | |
H3 | 0.5819 | 0.6658 | 0.1662 | 0.031* | |
N4 | 0.4845 (4) | 0.59019 (15) | 0.24245 (13) | 0.0250 (9) | |
H4N | 0.5634 | 0.6067 | 0.2345 | 0.030* | |
N5 | 0.4659 (4) | 0.62382 (16) | 0.33677 (13) | 0.0241 (8) | |
H5 | 0.3893 | 0.6330 | 0.3220 | 0.029* | |
N6 | 0.4176 (4) | 0.58452 (16) | 0.42480 (12) | 0.0229 (8) | |
H6 | 0.3603 | 0.5773 | 0.4019 | 0.028* | |
N7 | 0.6405 (4) | 0.51027 (16) | 0.44540 (13) | 0.0235 (8) | |
H7 | 0.6144 | 0.5162 | 0.4168 | 0.028* | |
N8 | 0.8594 (4) | 0.58549 (16) | 0.43117 (12) | 0.0231 (8) | |
H8 | 0.7744 | 0.5970 | 0.4374 | 0.028* | |
N9 | 0.9410 (4) | 0.59572 (17) | 0.33834 (13) | 0.0263 (9) | |
H9N | 0.8529 | 0.5930 | 0.3459 | 0.032* | |
C1 | 1.0742 (6) | 0.7023 (2) | 0.26951 (19) | 0.0346 (12) | |
H1A | 1.1540 | 0.6792 | 0.2579 | 0.042* | |
H1B | 1.0773 | 0.7030 | 0.3035 | 0.042* | |
C2 | 1.0744 (6) | 0.7641 (2) | 0.24993 (19) | 0.0371 (12) | |
H2A | 1.1268 | 0.7915 | 0.2699 | 0.044* | |
H2B | 1.1148 | 0.7648 | 0.2187 | 0.044* | |
C3 | 0.9219 (6) | 0.7797 (2) | 0.24890 (18) | 0.0329 (11) | |
H3A | 0.9037 | 0.8125 | 0.2273 | 0.039* | |
H3B | 0.8882 | 0.7908 | 0.2799 | 0.039* | |
C4 | 0.8534 (5) | 0.7222 (2) | 0.23222 (17) | 0.0287 (11) | |
H4 | 0.7565 | 0.7189 | 0.2441 | 0.034* | |
C5 | 0.8555 (5) | 0.71933 (19) | 0.17980 (17) | 0.0280 (11) | |
C6 | 0.7463 (6) | 0.7547 (2) | 0.10845 (16) | 0.0342 (12) | |
H6A | 0.7449 | 0.7170 | 0.0913 | 0.041* | |
H6B | 0.8296 | 0.7773 | 0.0994 | 0.041* | |
C7 | 0.6159 (6) | 0.7898 (2) | 0.09956 (18) | 0.0382 (13) | |
H7A | 0.5371 | 0.7635 | 0.0922 | 0.046* | |
H7B | 0.6294 | 0.8179 | 0.0739 | 0.046* | |
C8 | 0.5911 (6) | 0.8225 (2) | 0.14493 (17) | 0.0337 (12) | |
H8A | 0.4931 | 0.8348 | 0.1480 | 0.040* | |
H8B | 0.6514 | 0.8576 | 0.1475 | 0.040* | |
C9 | 0.6295 (5) | 0.7757 (2) | 0.18099 (16) | 0.0277 (11) | |
H9 | 0.6636 | 0.7955 | 0.2095 | 0.033* | |
C10 | 0.5051 (5) | 0.7374 (2) | 0.19241 (16) | 0.0272 (11) | |
C11 | 0.3796 (5) | 0.6465 (2) | 0.17925 (16) | 0.0268 (10) | |
H11 | 0.2998 | 0.6746 | 0.1808 | 0.032* | |
C12 | 0.3674 (5) | 0.6048 (2) | 0.22016 (16) | 0.0270 (11) | |
C13 | 0.3627 (5) | 0.6099 (2) | 0.13493 (16) | 0.0261 (10) | |
H13A | 0.4444 | 0.5840 | 0.1312 | 0.031* | |
H13B | 0.2798 | 0.5845 | 0.1379 | 0.031* | |
C14 | 0.3478 (5) | 0.6482 (2) | 0.09237 (15) | 0.0265 (10) | |
C15 | 0.4476 (6) | 0.6463 (2) | 0.05815 (16) | 0.0313 (11) | |
H15 | 0.5263 | 0.6216 | 0.0616 | 0.038* | |
C16 | 0.4331 (7) | 0.6806 (2) | 0.01861 (18) | 0.0403 (14) | |
H16 | 0.5010 | 0.6787 | −0.0050 | 0.048* | |
C17 | 0.3207 (7) | 0.7169 (2) | 0.01388 (19) | 0.0430 (15) | |
H17 | 0.3121 | 0.7412 | −0.0126 | 0.052* | |
C18 | 0.2198 (7) | 0.7183 (2) | 0.04750 (19) | 0.0423 (14) | |
H18 | 0.1401 | 0.7423 | 0.0436 | 0.051* | |
C19 | 0.2348 (6) | 0.6847 (2) | 0.08716 (17) | 0.0325 (12) | |
H19 | 0.1668 | 0.6868 | 0.1107 | 0.039* | |
C20 | 0.4821 (5) | 0.54731 (19) | 0.27970 (15) | 0.0236 (10) | |
H20 | 0.3830 | 0.5368 | 0.2854 | 0.028* | |
C21 | 0.5373 (5) | 0.57641 (19) | 0.32338 (15) | 0.0221 (10) | |
C22 | 0.5582 (5) | 0.4906 (2) | 0.26685 (16) | 0.0287 (11) | |
H22A | 0.6562 | 0.4996 | 0.2597 | 0.034* | |
H22B | 0.5562 | 0.4628 | 0.2931 | 0.034* | |
C23 | 0.4892 (6) | 0.46284 (19) | 0.22550 (17) | 0.0294 (11) | |
C24 | 0.5391 (6) | 0.4724 (2) | 0.18170 (17) | 0.0348 (12) | |
H24 | 0.6233 | 0.4934 | 0.1775 | 0.042* | |
C25 | 0.4671 (7) | 0.4515 (2) | 0.14341 (18) | 0.0450 (15) | |
H25 | 0.5032 | 0.4578 | 0.1134 | 0.054* | |
C26 | 0.3453 (7) | 0.4220 (2) | 0.1488 (2) | 0.0457 (15) | |
H26 | 0.2955 | 0.4090 | 0.1226 | 0.055* | |
C27 | 0.2942 (6) | 0.4111 (2) | 0.1919 (2) | 0.0421 (14) | |
H27 | 0.2107 | 0.3894 | 0.1956 | 0.050* | |
C28 | 0.3660 (6) | 0.4320 (2) | 0.23042 (19) | 0.0356 (12) | |
H28 | 0.3298 | 0.4251 | 0.2603 | 0.043* | |
C29 | 0.5101 (5) | 0.66102 (19) | 0.37490 (15) | 0.0239 (10) | |
H29 | 0.6081 | 0.6730 | 0.3689 | 0.029* | |
C30 | 0.5073 (5) | 0.62878 (19) | 0.42061 (15) | 0.0232 (10) | |
C31 | 0.4234 (5) | 0.7166 (2) | 0.37657 (16) | 0.0266 (10) | |
H31A | 0.4553 | 0.7409 | 0.4027 | 0.032* | |
H31B | 0.3260 | 0.7054 | 0.3826 | 0.032* | |
C32 | 0.4282 (5) | 0.7545 (2) | 0.33260 (16) | 0.0282 (11) | |
H32 | 0.3818 | 0.7319 | 0.3074 | 0.034* | |
C33 | 0.5744 (6) | 0.7671 (2) | 0.31781 (19) | 0.0409 (13) | |
H33A | 0.5734 | 0.7940 | 0.2915 | 0.061* | |
H33B | 0.6199 | 0.7302 | 0.3090 | 0.061* | |
H33C | 0.6252 | 0.7852 | 0.3433 | 0.061* | |
C34 | 0.3463 (6) | 0.8111 (2) | 0.3403 (2) | 0.0401 (13) | |
H34A | 0.3896 | 0.8340 | 0.3650 | 0.060* | |
H34B | 0.2509 | 0.8013 | 0.3490 | 0.060* | |
H34C | 0.3457 | 0.8344 | 0.3120 | 0.060* | |
C35 | 0.4103 (5) | 0.54745 (19) | 0.46583 (15) | 0.0232 (10) | |
H35 | 0.3765 | 0.5726 | 0.4917 | 0.028* | |
C36 | 0.5510 (5) | 0.52287 (19) | 0.47959 (16) | 0.0251 (10) | |
C37 | 0.3024 (5) | 0.4991 (2) | 0.45781 (16) | 0.0249 (10) | |
H37 | 0.2137 | 0.5196 | 0.4501 | 0.030* | |
C38 | 0.2740 (6) | 0.4624 (2) | 0.50061 (17) | 0.0327 (11) | |
H38A | 0.2051 | 0.4316 | 0.4929 | 0.039* | |
H38B | 0.3607 | 0.4423 | 0.5099 | 0.039* | |
C39 | 0.2204 (7) | 0.4982 (2) | 0.5410 (2) | 0.0447 (15) | |
H39A | 0.2927 | 0.5253 | 0.5515 | 0.067* | |
H39B | 0.1952 | 0.4715 | 0.5662 | 0.067* | |
H39C | 0.1387 | 0.5207 | 0.5315 | 0.067* | |
C40 | 0.3364 (6) | 0.4590 (2) | 0.41696 (17) | 0.0317 (11) | |
H40A | 0.4194 | 0.4358 | 0.4239 | 0.048* | |
H40B | 0.3531 | 0.4831 | 0.3896 | 0.048* | |
H40C | 0.2583 | 0.4323 | 0.4113 | 0.048* | |
C41 | 0.7780 (5) | 0.4874 (2) | 0.45410 (17) | 0.0255 (10) | |
H41 | 0.7903 | 0.4870 | 0.4882 | 0.031* | |
C42 | 0.8912 (5) | 0.5279 (2) | 0.43471 (16) | 0.0249 (10) | |
C43 | 0.7972 (5) | 0.4237 (2) | 0.43773 (18) | 0.0321 (11) | |
H43 | 0.8966 | 0.4128 | 0.4424 | 0.039* | |
C44 | 0.7639 (6) | 0.4165 (2) | 0.38658 (19) | 0.0361 (12) | |
H44A | 0.6622 | 0.4185 | 0.3825 | 0.043* | |
H44B | 0.8051 | 0.4499 | 0.3695 | 0.043* | |
C45 | 0.8158 (7) | 0.3598 (3) | 0.3658 (2) | 0.0533 (16) | |
H45A | 0.9169 | 0.3582 | 0.3684 | 0.080* | |
H45B | 0.7892 | 0.3581 | 0.3333 | 0.080* | |
H45C | 0.7749 | 0.3263 | 0.3822 | 0.080* | |
C46 | 0.7089 (6) | 0.3826 (2) | 0.4677 (2) | 0.0411 (13) | |
H46A | 0.6113 | 0.3940 | 0.4653 | 0.062* | |
H46B | 0.7391 | 0.3857 | 0.4998 | 0.062* | |
H46C | 0.7201 | 0.3419 | 0.4571 | 0.062* | |
C47 | 0.9618 (5) | 0.62935 (19) | 0.41727 (16) | 0.0252 (10) | |
H47 | 0.9096 | 0.6667 | 0.4114 | 0.030* | |
C48 | 1.0320 (5) | 0.6122 (2) | 0.37119 (16) | 0.0258 (10) | |
C49 | 1.0681 (5) | 0.6434 (2) | 0.45468 (16) | 0.0263 (10) | |
H49A | 1.1323 | 0.6096 | 0.4575 | 0.032* | |
H49B | 1.1232 | 0.6779 | 0.4448 | 0.032* | |
C50 | 1.0069 (5) | 0.6563 (2) | 0.50175 (17) | 0.0307 (11) | |
H50 | 0.9595 | 0.6198 | 0.5128 | 0.037* | |
C51 | 0.9008 (6) | 0.7058 (3) | 0.5012 (2) | 0.0436 (14) | |
H51A | 0.9432 | 0.7415 | 0.4884 | 0.065* | |
H51B | 0.8691 | 0.7136 | 0.5326 | 0.065* | |
H51C | 0.8216 | 0.6942 | 0.4821 | 0.065* | |
C52 | 1.1236 (6) | 0.6707 (2) | 0.53541 (18) | 0.0351 (12) | |
H52A | 1.1963 | 0.6407 | 0.5330 | 0.053* | |
H52B | 1.0869 | 0.6712 | 0.5668 | 0.053* | |
H52C | 1.1625 | 0.7095 | 0.5280 | 0.053* | |
C53 | 0.9795 (5) | 0.5821 (2) | 0.29114 (16) | 0.0285 (11) | |
H53 | 1.0796 | 0.5917 | 0.2865 | 0.034* | |
C54 | 0.8905 (5) | 0.6238 (2) | 0.26157 (16) | 0.0273 (11) | |
C55 | 0.9558 (5) | 0.5164 (2) | 0.28067 (17) | 0.0303 (11) | |
H55 | 0.8601 | 0.5058 | 0.2909 | 0.036* | |
C56 | 1.0589 (6) | 0.4799 (2) | 0.30845 (18) | 0.0357 (12) | |
H56A | 1.0401 | 0.4379 | 0.3037 | 0.054* | |
H56B | 1.0494 | 0.4895 | 0.3412 | 0.054* | |
H56C | 1.1533 | 0.4890 | 0.2983 | 0.054* | |
C57 | 0.9683 (6) | 0.5025 (2) | 0.22992 (18) | 0.0388 (13) | |
H57A | 0.8995 | 0.5253 | 0.2127 | 0.058* | |
H57B | 0.9520 | 0.4603 | 0.2250 | 0.058* | |
H57C | 1.0614 | 0.5128 | 0.2192 | 0.058* | |
C1S | 0.8290 (6) | 0.5854 (2) | 0.12039 (18) | 0.0355 (12) | |
C2S | 0.9706 (6) | 0.5686 (3) | 0.1108 (2) | 0.0489 (15) | |
H2S1 | 0.9714 | 0.5339 | 0.0908 | 0.073* | |
H2S2 | 1.0179 | 0.5593 | 0.1397 | 0.073* | |
H2S3 | 1.0183 | 0.6013 | 0.0955 | 0.073* | |
C3S | 0.4920 (9) | 0.6854 (3) | 0.5991 (3) | 0.068 (2) | |
C4S | 0.5619 (11) | 0.6418 (4) | 0.5704 (3) | 0.088 (3) | |
H4S1 | 0.5633 | 0.6555 | 0.5385 | 0.131* | |
H4S2 | 0.5121 | 0.6042 | 0.5722 | 0.131* | |
H4S3 | 0.6571 | 0.6364 | 0.5813 | 0.131* | |
N1S | 0.7185 (5) | 0.5986 (2) | 0.12775 (17) | 0.0437 (12) | |
N2S | 0.4386 (8) | 0.7210 (3) | 0.6218 (2) | 0.086 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.034 (2) | 0.0395 (19) | 0.032 (2) | 0.0004 (16) | 0.0068 (16) | −0.0039 (15) |
O2 | 0.041 (2) | 0.0338 (18) | 0.036 (2) | 0.0014 (16) | 0.0054 (16) | −0.0083 (16) |
O3 | 0.024 (2) | 0.048 (2) | 0.033 (2) | −0.0012 (16) | 0.0033 (15) | 0.0133 (16) |
O4 | 0.0266 (18) | 0.0322 (16) | 0.0188 (17) | 0.0017 (14) | −0.0005 (14) | −0.0004 (13) |
O5 | 0.0324 (19) | 0.0253 (15) | 0.0234 (18) | −0.0024 (14) | −0.0041 (14) | −0.0028 (13) |
O6 | 0.033 (2) | 0.0434 (19) | 0.0199 (19) | 0.0029 (16) | −0.0015 (14) | 0.0056 (14) |
O7 | 0.0212 (19) | 0.0322 (17) | 0.036 (2) | 0.0024 (15) | −0.0032 (14) | −0.0001 (14) |
O8 | 0.024 (2) | 0.0426 (19) | 0.0262 (18) | −0.0033 (15) | −0.0004 (14) | −0.0019 (15) |
O9 | 0.029 (2) | 0.0381 (18) | 0.0311 (19) | −0.0088 (15) | −0.0047 (15) | 0.0056 (15) |
N1 | 0.024 (2) | 0.033 (2) | 0.027 (2) | −0.0026 (17) | −0.0006 (17) | −0.0008 (17) |
N2 | 0.035 (2) | 0.028 (2) | 0.025 (2) | 0.0025 (18) | 0.0012 (17) | 0.0008 (17) |
N3 | 0.029 (2) | 0.0278 (19) | 0.019 (2) | 0.0003 (17) | 0.0026 (16) | 0.0006 (15) |
N4 | 0.028 (2) | 0.0234 (18) | 0.024 (2) | −0.0012 (16) | −0.0006 (16) | −0.0006 (15) |
N5 | 0.026 (2) | 0.0272 (19) | 0.019 (2) | 0.0025 (17) | −0.0039 (16) | 0.0006 (15) |
N6 | 0.025 (2) | 0.0258 (19) | 0.0182 (19) | −0.0008 (17) | −0.0027 (15) | 0.0013 (15) |
N7 | 0.024 (2) | 0.0261 (19) | 0.020 (2) | −0.0001 (17) | −0.0013 (16) | −0.0015 (15) |
N8 | 0.020 (2) | 0.0252 (19) | 0.024 (2) | 0.0009 (16) | −0.0025 (16) | −0.0019 (15) |
N9 | 0.023 (2) | 0.033 (2) | 0.022 (2) | −0.0006 (17) | 0.0016 (16) | −0.0022 (16) |
C1 | 0.031 (3) | 0.035 (3) | 0.038 (3) | −0.004 (2) | −0.003 (2) | 0.000 (2) |
C2 | 0.043 (3) | 0.034 (3) | 0.034 (3) | −0.006 (2) | −0.007 (2) | −0.001 (2) |
C3 | 0.039 (3) | 0.030 (2) | 0.029 (3) | 0.000 (2) | −0.004 (2) | −0.002 (2) |
C4 | 0.028 (3) | 0.031 (2) | 0.027 (3) | 0.003 (2) | −0.001 (2) | 0.0010 (19) |
C5 | 0.031 (3) | 0.024 (2) | 0.030 (3) | −0.003 (2) | 0.001 (2) | 0.000 (2) |
C6 | 0.047 (3) | 0.037 (3) | 0.018 (3) | −0.003 (2) | 0.002 (2) | 0.003 (2) |
C7 | 0.053 (4) | 0.034 (3) | 0.027 (3) | −0.007 (2) | −0.005 (2) | 0.004 (2) |
C8 | 0.041 (3) | 0.027 (2) | 0.033 (3) | 0.002 (2) | −0.001 (2) | 0.007 (2) |
C9 | 0.033 (3) | 0.023 (2) | 0.026 (3) | 0.004 (2) | −0.002 (2) | −0.0024 (19) |
C10 | 0.034 (3) | 0.027 (2) | 0.021 (2) | 0.002 (2) | −0.001 (2) | 0.0018 (19) |
C11 | 0.028 (3) | 0.029 (2) | 0.023 (2) | −0.004 (2) | −0.0011 (19) | 0.0024 (19) |
C12 | 0.031 (3) | 0.028 (2) | 0.022 (2) | 0.003 (2) | 0.001 (2) | −0.0060 (19) |
C13 | 0.029 (3) | 0.027 (2) | 0.023 (2) | −0.002 (2) | −0.003 (2) | 0.0017 (19) |
C14 | 0.036 (3) | 0.023 (2) | 0.021 (2) | −0.005 (2) | −0.003 (2) | −0.0002 (18) |
C15 | 0.044 (3) | 0.026 (2) | 0.024 (3) | −0.005 (2) | 0.003 (2) | 0.000 (2) |
C16 | 0.060 (4) | 0.036 (3) | 0.024 (3) | −0.013 (3) | 0.004 (3) | −0.003 (2) |
C17 | 0.076 (5) | 0.028 (3) | 0.025 (3) | −0.009 (3) | −0.007 (3) | 0.005 (2) |
C18 | 0.059 (4) | 0.034 (3) | 0.034 (3) | 0.006 (3) | −0.013 (3) | 0.002 (2) |
C19 | 0.039 (3) | 0.030 (3) | 0.028 (3) | −0.001 (2) | −0.003 (2) | 0.000 (2) |
C20 | 0.028 (3) | 0.023 (2) | 0.019 (2) | −0.0024 (19) | −0.0014 (19) | 0.0022 (17) |
C21 | 0.024 (3) | 0.024 (2) | 0.019 (2) | −0.0009 (19) | 0.0017 (19) | 0.0051 (18) |
C22 | 0.034 (3) | 0.027 (2) | 0.025 (3) | 0.003 (2) | −0.006 (2) | −0.0001 (19) |
C23 | 0.040 (3) | 0.021 (2) | 0.027 (3) | 0.006 (2) | −0.003 (2) | −0.0034 (18) |
C24 | 0.052 (4) | 0.024 (2) | 0.028 (3) | 0.003 (2) | 0.002 (2) | −0.001 (2) |
C25 | 0.076 (5) | 0.036 (3) | 0.022 (3) | 0.019 (3) | −0.002 (3) | −0.002 (2) |
C26 | 0.067 (4) | 0.029 (3) | 0.042 (3) | 0.009 (3) | −0.019 (3) | −0.011 (2) |
C27 | 0.044 (4) | 0.028 (3) | 0.055 (4) | 0.004 (2) | −0.014 (3) | −0.013 (2) |
C28 | 0.043 (3) | 0.025 (2) | 0.038 (3) | 0.002 (2) | −0.001 (2) | −0.005 (2) |
C29 | 0.027 (3) | 0.025 (2) | 0.019 (2) | −0.0042 (19) | 0.0006 (19) | −0.0019 (17) |
C30 | 0.022 (3) | 0.026 (2) | 0.022 (2) | 0.0018 (19) | 0.0002 (19) | −0.0060 (17) |
C31 | 0.030 (3) | 0.026 (2) | 0.023 (3) | −0.001 (2) | 0.002 (2) | −0.0017 (18) |
C32 | 0.036 (3) | 0.026 (2) | 0.022 (2) | −0.002 (2) | −0.004 (2) | −0.0005 (19) |
C33 | 0.054 (4) | 0.037 (3) | 0.032 (3) | −0.007 (3) | 0.006 (3) | 0.006 (2) |
C34 | 0.054 (4) | 0.026 (2) | 0.040 (3) | 0.000 (2) | −0.012 (3) | 0.002 (2) |
C35 | 0.026 (3) | 0.025 (2) | 0.018 (2) | 0.001 (2) | 0.0031 (19) | 0.0001 (18) |
C36 | 0.029 (3) | 0.023 (2) | 0.023 (3) | −0.0001 (19) | −0.002 (2) | −0.0004 (18) |
C37 | 0.023 (3) | 0.025 (2) | 0.027 (3) | 0.0028 (19) | 0.0005 (19) | −0.0011 (19) |
C38 | 0.035 (3) | 0.030 (2) | 0.033 (3) | −0.002 (2) | 0.005 (2) | 0.006 (2) |
C39 | 0.062 (4) | 0.036 (3) | 0.037 (3) | −0.005 (3) | 0.017 (3) | 0.007 (2) |
C40 | 0.034 (3) | 0.030 (2) | 0.032 (3) | −0.001 (2) | −0.003 (2) | −0.005 (2) |
C41 | 0.023 (3) | 0.029 (2) | 0.024 (3) | 0.002 (2) | −0.0027 (19) | 0.0009 (19) |
C42 | 0.022 (3) | 0.030 (2) | 0.022 (2) | −0.003 (2) | −0.0058 (19) | −0.0002 (19) |
C43 | 0.029 (3) | 0.027 (2) | 0.041 (3) | 0.003 (2) | −0.001 (2) | 0.003 (2) |
C44 | 0.033 (3) | 0.030 (2) | 0.046 (3) | −0.005 (2) | 0.001 (2) | −0.006 (2) |
C45 | 0.057 (4) | 0.037 (3) | 0.066 (4) | 0.002 (3) | 0.004 (3) | −0.017 (3) |
C46 | 0.041 (3) | 0.028 (3) | 0.055 (4) | −0.002 (2) | 0.002 (3) | 0.005 (2) |
C47 | 0.029 (3) | 0.021 (2) | 0.027 (3) | 0.0000 (19) | 0.001 (2) | −0.0010 (18) |
C48 | 0.029 (3) | 0.026 (2) | 0.023 (2) | −0.002 (2) | −0.003 (2) | 0.0026 (18) |
C49 | 0.027 (3) | 0.026 (2) | 0.027 (3) | −0.003 (2) | 0.000 (2) | −0.0027 (19) |
C50 | 0.032 (3) | 0.033 (2) | 0.027 (3) | −0.003 (2) | −0.003 (2) | −0.002 (2) |
C51 | 0.046 (4) | 0.047 (3) | 0.037 (3) | 0.009 (3) | −0.009 (3) | −0.017 (3) |
C52 | 0.040 (3) | 0.035 (3) | 0.030 (3) | 0.001 (2) | −0.005 (2) | −0.004 (2) |
C53 | 0.028 (3) | 0.031 (2) | 0.026 (3) | −0.003 (2) | −0.001 (2) | −0.003 (2) |
C54 | 0.026 (3) | 0.035 (3) | 0.021 (2) | −0.001 (2) | 0.0046 (19) | −0.0010 (19) |
C55 | 0.030 (3) | 0.032 (2) | 0.029 (3) | −0.001 (2) | 0.002 (2) | −0.004 (2) |
C56 | 0.037 (3) | 0.035 (3) | 0.035 (3) | 0.003 (2) | 0.004 (2) | −0.005 (2) |
C57 | 0.042 (3) | 0.045 (3) | 0.030 (3) | −0.001 (2) | 0.000 (2) | −0.009 (2) |
C1S | 0.037 (4) | 0.040 (3) | 0.029 (3) | −0.005 (3) | −0.003 (2) | −0.002 (2) |
C2S | 0.038 (4) | 0.060 (4) | 0.049 (4) | 0.003 (3) | 0.006 (3) | −0.015 (3) |
C3S | 0.090 (6) | 0.062 (4) | 0.052 (4) | 0.002 (4) | −0.004 (4) | −0.006 (4) |
C4S | 0.117 (7) | 0.080 (5) | 0.066 (5) | 0.007 (5) | −0.016 (5) | −0.029 (4) |
N1S | 0.036 (3) | 0.045 (3) | 0.049 (3) | 0.000 (2) | 0.001 (2) | 0.001 (2) |
N2S | 0.109 (6) | 0.086 (5) | 0.062 (4) | 0.022 (4) | −0.001 (4) | −0.008 (4) |
O1—C5 | 1.221 (6) | C26—C27 | 1.369 (9) |
O2—C10 | 1.233 (6) | C26—H26 | 0.9500 |
O3—C12 | 1.226 (6) | C27—C28 | 1.402 (8) |
O4—C21 | 1.232 (5) | C27—H27 | 0.9500 |
O5—C30 | 1.240 (5) | C28—H28 | 0.9500 |
O6—C36 | 1.226 (6) | C29—C31 | 1.514 (7) |
O7—C42 | 1.223 (6) | C29—C30 | 1.518 (6) |
O8—C48 | 1.220 (6) | C29—H29 | 1.0000 |
O9—C54 | 1.229 (6) | C31—C32 | 1.542 (6) |
N1—C54 | 1.340 (6) | C31—H31A | 0.9900 |
N1—C4 | 1.462 (6) | C31—H31B | 0.9900 |
N1—C1 | 1.470 (7) | C32—C33 | 1.503 (8) |
N2—C5 | 1.355 (6) | C32—C34 | 1.525 (7) |
N2—C9 | 1.472 (6) | C32—H32 | 1.0000 |
N2—C6 | 1.484 (6) | C33—H33A | 0.9800 |
N3—C10 | 1.347 (6) | C33—H33B | 0.9800 |
N3—C11 | 1.449 (6) | C33—H33C | 0.9800 |
N3—H3 | 0.8800 | C34—H34A | 0.9800 |
N4—C12 | 1.345 (6) | C34—H34B | 0.9800 |
N4—C20 | 1.457 (6) | C34—H34C | 0.9800 |
N4—H4N | 0.8800 | C35—C36 | 1.522 (7) |
N5—C21 | 1.336 (6) | C35—C37 | 1.530 (6) |
N5—C29 | 1.458 (6) | C35—H35 | 1.0000 |
N5—H5 | 0.8800 | C37—C38 | 1.523 (7) |
N6—C30 | 1.332 (6) | C37—C40 | 1.533 (7) |
N6—C35 | 1.462 (6) | C37—H37 | 1.0000 |
N6—H6 | 0.8800 | C38—C39 | 1.520 (8) |
N7—C36 | 1.348 (6) | C38—H38A | 0.9900 |
N7—C41 | 1.448 (6) | C38—H38B | 0.9900 |
N7—H7 | 0.8800 | C39—H39A | 0.9800 |
N8—C42 | 1.346 (6) | C39—H39B | 0.9800 |
N8—C47 | 1.460 (6) | C39—H39C | 0.9800 |
N8—H8 | 0.8800 | C40—H40A | 0.9800 |
N9—C48 | 1.351 (6) | C40—H40B | 0.9800 |
N9—C53 | 1.456 (6) | C40—H40C | 0.9800 |
N9—H9N | 0.8800 | C41—C43 | 1.533 (7) |
C1—C2 | 1.515 (7) | C41—C42 | 1.536 (7) |
C1—H1A | 0.9900 | C41—H41 | 1.0000 |
C1—H1B | 0.9900 | C43—C44 | 1.531 (8) |
C2—C3 | 1.514 (8) | C43—C46 | 1.535 (7) |
C2—H2A | 0.9900 | C43—H43 | 1.0000 |
C2—H2B | 0.9900 | C44—C45 | 1.506 (7) |
C3—C4 | 1.541 (7) | C44—H44A | 0.9900 |
C3—H3A | 0.9900 | C44—H44B | 0.9900 |
C3—H3B | 0.9900 | C45—H45A | 0.9800 |
C4—C5 | 1.527 (7) | C45—H45B | 0.9800 |
C4—H4 | 1.0000 | C45—H45C | 0.9800 |
C6—C7 | 1.512 (8) | C46—H46A | 0.9800 |
C6—H6A | 0.9900 | C46—H46B | 0.9800 |
C6—H6B | 0.9900 | C46—H46C | 0.9800 |
C7—C8 | 1.533 (7) | C47—C49 | 1.529 (7) |
C7—H7A | 0.9900 | C47—C48 | 1.552 (7) |
C7—H7B | 0.9900 | C47—H47 | 1.0000 |
C8—C9 | 1.538 (7) | C49—C50 | 1.520 (7) |
C8—H8A | 0.9900 | C49—H49A | 0.9900 |
C8—H8B | 0.9900 | C49—H49B | 0.9900 |
C9—C10 | 1.519 (7) | C50—C51 | 1.520 (8) |
C9—H9 | 1.0000 | C50—C52 | 1.528 (7) |
C11—C12 | 1.526 (7) | C50—H50 | 1.0000 |
C11—C13 | 1.542 (7) | C51—H51A | 0.9800 |
C11—H11 | 1.0000 | C51—H51B | 0.9800 |
C13—C14 | 1.519 (6) | C51—H51C | 0.9800 |
C13—H13A | 0.9900 | C52—H52A | 0.9800 |
C13—H13B | 0.9900 | C52—H52B | 0.9800 |
C14—C19 | 1.378 (7) | C52—H52C | 0.9800 |
C14—C15 | 1.386 (7) | C53—C55 | 1.538 (7) |
C15—C16 | 1.396 (7) | C53—C54 | 1.541 (7) |
C15—H15 | 0.9500 | C53—H53 | 1.0000 |
C16—C17 | 1.370 (9) | C55—C57 | 1.515 (7) |
C16—H16 | 0.9500 | C55—C56 | 1.526 (7) |
C17—C18 | 1.380 (9) | C55—H55 | 1.0000 |
C17—H17 | 0.9500 | C56—H56A | 0.9800 |
C18—C19 | 1.391 (7) | C56—H56B | 0.9800 |
C18—H18 | 0.9500 | C56—H56C | 0.9800 |
C19—H19 | 0.9500 | C57—H57A | 0.9800 |
C20—C22 | 1.528 (6) | C57—H57B | 0.9800 |
C20—C21 | 1.528 (6) | C57—H57C | 0.9800 |
C20—H20 | 1.0000 | C1S—N1S | 1.128 (7) |
C22—C23 | 1.513 (7) | C1S—C2S | 1.445 (9) |
C22—H22A | 0.9900 | C2S—H2S1 | 0.9800 |
C22—H22B | 0.9900 | C2S—H2S2 | 0.9800 |
C23—C24 | 1.380 (7) | C2S—H2S3 | 0.9800 |
C23—C28 | 1.387 (8) | C3S—N2S | 1.164 (10) |
C24—C25 | 1.397 (8) | C3S—C4S | 1.458 (11) |
C24—H24 | 0.9500 | C4S—H4S1 | 0.9800 |
C25—C26 | 1.361 (9) | C4S—H4S2 | 0.9800 |
C25—H25 | 0.9500 | C4S—H4S3 | 0.9800 |
C54—N1—C4 | 119.1 (4) | C32—C31—H31B | 108.5 |
C54—N1—C1 | 127.7 (4) | H31A—C31—H31B | 107.5 |
C4—N1—C1 | 112.2 (4) | C33—C32—C34 | 111.7 (4) |
C5—N2—C9 | 126.8 (4) | C33—C32—C31 | 111.8 (4) |
C5—N2—C6 | 120.2 (4) | C34—C32—C31 | 109.4 (4) |
C9—N2—C6 | 111.3 (4) | C33—C32—H32 | 108.0 |
C10—N3—C11 | 120.1 (4) | C34—C32—H32 | 108.0 |
C10—N3—H3 | 120.0 | C31—C32—H32 | 108.0 |
C11—N3—H3 | 120.0 | C32—C33—H33A | 109.5 |
C12—N4—C20 | 120.6 (4) | C32—C33—H33B | 109.5 |
C12—N4—H4N | 119.7 | H33A—C33—H33B | 109.5 |
C20—N4—H4N | 119.7 | C32—C33—H33C | 109.5 |
C21—N5—C29 | 122.5 (4) | H33A—C33—H33C | 109.5 |
C21—N5—H5 | 118.7 | H33B—C33—H33C | 109.5 |
C29—N5—H5 | 118.7 | C32—C34—H34A | 109.5 |
C30—N6—C35 | 122.7 (4) | C32—C34—H34B | 109.5 |
C30—N6—H6 | 118.7 | H34A—C34—H34B | 109.5 |
C35—N6—H6 | 118.7 | C32—C34—H34C | 109.5 |
C36—N7—C41 | 122.3 (4) | H34A—C34—H34C | 109.5 |
C36—N7—H7 | 118.8 | H34B—C34—H34C | 109.5 |
C41—N7—H7 | 118.8 | N6—C35—C36 | 112.5 (4) |
C42—N8—C47 | 121.9 (4) | N6—C35—C37 | 108.7 (4) |
C42—N8—H8 | 119.0 | C36—C35—C37 | 112.6 (4) |
C47—N8—H8 | 119.0 | N6—C35—H35 | 107.6 |
C48—N9—C53 | 124.0 (4) | C36—C35—H35 | 107.6 |
C48—N9—H9N | 118.0 | C37—C35—H35 | 107.6 |
C53—N9—H9N | 118.0 | O6—C36—N7 | 123.4 (5) |
N1—C1—C2 | 103.5 (4) | O6—C36—C35 | 119.5 (4) |
N1—C1—H1A | 111.1 | N7—C36—C35 | 117.1 (4) |
C2—C1—H1A | 111.1 | C38—C37—C35 | 113.0 (4) |
N1—C1—H1B | 111.1 | C38—C37—C40 | 110.3 (4) |
C2—C1—H1B | 111.1 | C35—C37—C40 | 113.5 (4) |
H1A—C1—H1B | 109.0 | C38—C37—H37 | 106.5 |
C3—C2—C1 | 102.8 (4) | C35—C37—H37 | 106.5 |
C3—C2—H2A | 111.2 | C40—C37—H37 | 106.5 |
C1—C2—H2A | 111.2 | C39—C38—C37 | 113.7 (4) |
C3—C2—H2B | 111.2 | C39—C38—H38A | 108.8 |
C1—C2—H2B | 111.2 | C37—C38—H38A | 108.8 |
H2A—C2—H2B | 109.1 | C39—C38—H38B | 108.8 |
C2—C3—C4 | 103.1 (4) | C37—C38—H38B | 108.8 |
C2—C3—H3A | 111.2 | H38A—C38—H38B | 107.7 |
C4—C3—H3A | 111.2 | C38—C39—H39A | 109.5 |
C2—C3—H3B | 111.2 | C38—C39—H39B | 109.5 |
C4—C3—H3B | 111.2 | H39A—C39—H39B | 109.5 |
H3A—C3—H3B | 109.1 | C38—C39—H39C | 109.5 |
N1—C4—C5 | 112.1 (4) | H39A—C39—H39C | 109.5 |
N1—C4—C3 | 101.8 (4) | H39B—C39—H39C | 109.5 |
C5—C4—C3 | 110.2 (4) | C37—C40—H40A | 109.5 |
N1—C4—H4 | 110.8 | C37—C40—H40B | 109.5 |
C5—C4—H4 | 110.8 | H40A—C40—H40B | 109.5 |
C3—C4—H4 | 110.8 | C37—C40—H40C | 109.5 |
O1—C5—N2 | 122.2 (5) | H40A—C40—H40C | 109.5 |
O1—C5—C4 | 122.6 (5) | H40B—C40—H40C | 109.5 |
N2—C5—C4 | 115.1 (4) | N7—C41—C43 | 113.2 (4) |
N2—C6—C7 | 104.2 (4) | N7—C41—C42 | 111.9 (4) |
N2—C6—H6A | 110.9 | C43—C41—C42 | 111.4 (4) |
C7—C6—H6A | 110.9 | N7—C41—H41 | 106.6 |
N2—C6—H6B | 110.9 | C43—C41—H41 | 106.6 |
C7—C6—H6B | 110.9 | C42—C41—H41 | 106.6 |
H6A—C6—H6B | 108.9 | O7—C42—N8 | 122.1 (4) |
C6—C7—C8 | 103.8 (4) | O7—C42—C41 | 121.3 (4) |
C6—C7—H7A | 111.0 | N8—C42—C41 | 116.6 (4) |
C8—C7—H7A | 111.0 | C44—C43—C41 | 112.2 (4) |
C6—C7—H7B | 111.0 | C44—C43—C46 | 111.8 (4) |
C8—C7—H7B | 111.0 | C41—C43—C46 | 109.2 (4) |
H7A—C7—H7B | 109.0 | C44—C43—H43 | 107.8 |
C7—C8—C9 | 102.5 (4) | C41—C43—H43 | 107.8 |
C7—C8—H8A | 111.3 | C46—C43—H43 | 107.8 |
C9—C8—H8A | 111.3 | C45—C44—C43 | 114.3 (5) |
C7—C8—H8B | 111.3 | C45—C44—H44A | 108.7 |
C9—C8—H8B | 111.3 | C43—C44—H44A | 108.7 |
H8A—C8—H8B | 109.2 | C45—C44—H44B | 108.7 |
N2—C9—C10 | 114.3 (4) | C43—C44—H44B | 108.7 |
N2—C9—C8 | 102.7 (4) | H44A—C44—H44B | 107.6 |
C10—C9—C8 | 110.7 (4) | C44—C45—H45A | 109.5 |
N2—C9—H9 | 109.6 | C44—C45—H45B | 109.5 |
C10—C9—H9 | 109.6 | H45A—C45—H45B | 109.5 |
C8—C9—H9 | 109.6 | C44—C45—H45C | 109.5 |
O2—C10—N3 | 123.5 (5) | H45A—C45—H45C | 109.5 |
O2—C10—C9 | 118.5 (4) | H45B—C45—H45C | 109.5 |
N3—C10—C9 | 117.9 (4) | C43—C46—H46A | 109.5 |
N3—C11—C12 | 115.7 (4) | C43—C46—H46B | 109.5 |
N3—C11—C13 | 110.4 (4) | H46A—C46—H46B | 109.5 |
C12—C11—C13 | 108.1 (4) | C43—C46—H46C | 109.5 |
N3—C11—H11 | 107.4 | H46A—C46—H46C | 109.5 |
C12—C11—H11 | 107.4 | H46B—C46—H46C | 109.5 |
C13—C11—H11 | 107.4 | N8—C47—C49 | 113.5 (4) |
O3—C12—N4 | 123.8 (4) | N8—C47—C48 | 111.4 (4) |
O3—C12—C11 | 118.5 (4) | C49—C47—C48 | 112.0 (4) |
N4—C12—C11 | 117.7 (4) | N8—C47—H47 | 106.5 |
C14—C13—C11 | 112.6 (4) | C49—C47—H47 | 106.5 |
C14—C13—H13A | 109.1 | C48—C47—H47 | 106.5 |
C11—C13—H13A | 109.1 | O8—C48—N9 | 124.4 (4) |
C14—C13—H13B | 109.1 | O8—C48—C47 | 122.0 (4) |
C11—C13—H13B | 109.1 | N9—C48—C47 | 113.4 (4) |
H13A—C13—H13B | 107.8 | C50—C49—C47 | 114.9 (4) |
C19—C14—C15 | 119.3 (4) | C50—C49—H49A | 108.5 |
C19—C14—C13 | 120.5 (5) | C47—C49—H49A | 108.5 |
C15—C14—C13 | 120.1 (4) | C50—C49—H49B | 108.5 |
C14—C15—C16 | 120.3 (5) | C47—C49—H49B | 108.5 |
C14—C15—H15 | 119.8 | H49A—C49—H49B | 107.5 |
C16—C15—H15 | 119.8 | C51—C50—C49 | 113.2 (4) |
C17—C16—C15 | 119.8 (5) | C51—C50—C52 | 110.2 (4) |
C17—C16—H16 | 120.1 | C49—C50—C52 | 109.4 (4) |
C15—C16—H16 | 120.1 | C51—C50—H50 | 107.9 |
C16—C17—C18 | 120.1 (5) | C49—C50—H50 | 107.9 |
C16—C17—H17 | 119.9 | C52—C50—H50 | 107.9 |
C18—C17—H17 | 119.9 | C50—C51—H51A | 109.5 |
C17—C18—C19 | 120.1 (6) | C50—C51—H51B | 109.5 |
C17—C18—H18 | 119.9 | H51A—C51—H51B | 109.5 |
C19—C18—H18 | 119.9 | C50—C51—H51C | 109.5 |
C14—C19—C18 | 120.2 (5) | H51A—C51—H51C | 109.5 |
C14—C19—H19 | 119.9 | H51B—C51—H51C | 109.5 |
C18—C19—H19 | 119.9 | C50—C52—H52A | 109.5 |
N4—C20—C22 | 111.9 (4) | C50—C52—H52B | 109.5 |
N4—C20—C21 | 108.9 (3) | H52A—C52—H52B | 109.5 |
C22—C20—C21 | 113.6 (4) | C50—C52—H52C | 109.5 |
N4—C20—H20 | 107.4 | H52A—C52—H52C | 109.5 |
C22—C20—H20 | 107.4 | H52B—C52—H52C | 109.5 |
C21—C20—H20 | 107.4 | N9—C53—C55 | 110.8 (4) |
O4—C21—N5 | 122.3 (4) | N9—C53—C54 | 104.7 (4) |
O4—C21—C20 | 123.4 (4) | C55—C53—C54 | 113.7 (4) |
N5—C21—C20 | 114.3 (4) | N9—C53—H53 | 109.2 |
C23—C22—C20 | 109.5 (4) | C55—C53—H53 | 109.2 |
C23—C22—H22A | 109.8 | C54—C53—H53 | 109.2 |
C20—C22—H22A | 109.8 | O9—C54—N1 | 122.4 (5) |
C23—C22—H22B | 109.8 | O9—C54—C53 | 120.5 (4) |
C20—C22—H22B | 109.8 | N1—C54—C53 | 116.9 (4) |
H22A—C22—H22B | 108.2 | C57—C55—C56 | 110.5 (4) |
C24—C23—C28 | 118.3 (5) | C57—C55—C53 | 112.6 (4) |
C24—C23—C22 | 121.0 (5) | C56—C55—C53 | 108.9 (4) |
C28—C23—C22 | 120.4 (5) | C57—C55—H55 | 108.2 |
C23—C24—C25 | 120.7 (5) | C56—C55—H55 | 108.2 |
C23—C24—H24 | 119.7 | C53—C55—H55 | 108.2 |
C25—C24—H24 | 119.7 | C55—C56—H56A | 109.5 |
C26—C25—C24 | 120.3 (5) | C55—C56—H56B | 109.5 |
C26—C25—H25 | 119.9 | H56A—C56—H56B | 109.5 |
C24—C25—H25 | 119.9 | C55—C56—H56C | 109.5 |
C25—C26—C27 | 120.5 (5) | H56A—C56—H56C | 109.5 |
C25—C26—H26 | 119.8 | H56B—C56—H56C | 109.5 |
C27—C26—H26 | 119.8 | C55—C57—H57A | 109.5 |
C26—C27—C28 | 119.5 (6) | C55—C57—H57B | 109.5 |
C26—C27—H27 | 120.3 | H57A—C57—H57B | 109.5 |
C28—C27—H27 | 120.3 | C55—C57—H57C | 109.5 |
C23—C28—C27 | 120.8 (5) | H57A—C57—H57C | 109.5 |
C23—C28—H28 | 119.6 | H57B—C57—H57C | 109.5 |
C27—C28—H28 | 119.6 | N1S—C1S—C2S | 179.8 (8) |
N5—C29—C31 | 110.2 (4) | C1S—C2S—H2S1 | 109.5 |
N5—C29—C30 | 112.5 (4) | C1S—C2S—H2S2 | 109.5 |
C31—C29—C30 | 111.3 (4) | H2S1—C2S—H2S2 | 109.5 |
N5—C29—H29 | 107.5 | C1S—C2S—H2S3 | 109.5 |
C31—C29—H29 | 107.5 | H2S1—C2S—H2S3 | 109.5 |
C30—C29—H29 | 107.5 | H2S2—C2S—H2S3 | 109.5 |
O5—C30—N6 | 122.7 (4) | N2S—C3S—C4S | 178.5 (10) |
O5—C30—C29 | 120.2 (4) | C3S—C4S—H4S1 | 109.5 |
N6—C30—C29 | 117.1 (4) | C3S—C4S—H4S2 | 109.5 |
C29—C31—C32 | 114.9 (4) | H4S1—C4S—H4S2 | 109.5 |
C29—C31—H31A | 108.5 | C3S—C4S—H4S3 | 109.5 |
C32—C31—H31A | 108.5 | H4S1—C4S—H4S3 | 109.5 |
C29—C31—H31B | 108.5 | H4S2—C4S—H4S3 | 109.5 |
C54—N1—C1—C2 | −178.5 (5) | C25—C26—C27—C28 | 2.1 (8) |
C4—N1—C1—C2 | −10.0 (5) | C24—C23—C28—C27 | 0.1 (7) |
N1—C1—C2—C3 | 31.4 (5) | C22—C23—C28—C27 | 173.7 (5) |
C1—C2—C3—C4 | −41.0 (5) | C26—C27—C28—C23 | −1.1 (7) |
C54—N1—C4—C5 | −87.7 (5) | C21—N5—C29—C31 | 170.1 (4) |
C1—N1—C4—C5 | 102.7 (5) | C21—N5—C29—C30 | −65.0 (5) |
C54—N1—C4—C3 | 154.5 (4) | C35—N6—C30—O5 | −2.3 (7) |
C1—N1—C4—C3 | −15.1 (5) | C35—N6—C30—C29 | 176.0 (4) |
C2—C3—C4—N1 | 34.2 (5) | N5—C29—C30—O5 | 151.1 (4) |
C2—C3—C4—C5 | −84.9 (5) | C31—C29—C30—O5 | −84.7 (5) |
C9—N2—C5—O1 | −172.3 (4) | N5—C29—C30—N6 | −27.2 (6) |
C6—N2—C5—O1 | −8.4 (7) | C31—C29—C30—N6 | 96.9 (5) |
C9—N2—C5—C4 | 4.1 (6) | N5—C29—C31—C32 | −58.5 (5) |
C6—N2—C5—C4 | 168.0 (4) | C30—C29—C31—C32 | 176.0 (4) |
N1—C4—C5—O1 | −25.4 (6) | C29—C31—C32—C33 | −51.3 (6) |
C3—C4—C5—O1 | 87.3 (5) | C29—C31—C32—C34 | −175.5 (4) |
N1—C4—C5—N2 | 158.3 (4) | C30—N6—C35—C36 | −51.3 (5) |
C3—C4—C5—N2 | −89.1 (5) | C30—N6—C35—C37 | −176.7 (4) |
C5—N2—C6—C7 | −172.2 (4) | C41—N7—C36—O6 | −2.6 (7) |
C9—N2—C6—C7 | −6.0 (5) | C41—N7—C36—C35 | 179.2 (4) |
N2—C6—C7—C8 | 28.2 (5) | N6—C35—C36—O6 | 148.2 (4) |
C6—C7—C8—C9 | −39.5 (5) | C37—C35—C36—O6 | −88.5 (5) |
C5—N2—C9—C10 | −93.4 (5) | N6—C35—C36—N7 | −33.5 (5) |
C6—N2—C9—C10 | 101.5 (5) | C37—C35—C36—N7 | 89.7 (5) |
C5—N2—C9—C8 | 146.6 (5) | N6—C35—C37—C38 | −173.1 (4) |
C6—N2—C9—C8 | −18.5 (5) | C36—C35—C37—C38 | 61.5 (5) |
C7—C8—C9—N2 | 35.1 (5) | N6—C35—C37—C40 | 60.4 (5) |
C7—C8—C9—C10 | −87.4 (5) | C36—C35—C37—C40 | −65.0 (5) |
C11—N3—C10—O2 | 9.1 (7) | C35—C37—C38—C39 | 59.7 (6) |
C11—N3—C10—C9 | −167.9 (4) | C40—C37—C38—C39 | −172.1 (5) |
N2—C9—C10—O2 | 176.2 (4) | C36—N7—C41—C43 | 112.4 (5) |
C8—C9—C10—O2 | −68.5 (6) | C36—N7—C41—C42 | −120.7 (4) |
N2—C9—C10—N3 | −6.7 (6) | C47—N8—C42—O7 | −4.2 (7) |
C8—C9—C10—N3 | 108.7 (5) | C47—N8—C42—C41 | 174.3 (4) |
C10—N3—C11—C12 | −98.5 (5) | N7—C41—C42—O7 | −154.2 (4) |
C10—N3—C11—C13 | 138.4 (4) | C43—C41—C42—O7 | −26.3 (6) |
C20—N4—C12—O3 | 1.7 (7) | N7—C41—C42—N8 | 27.3 (6) |
C20—N4—C12—C11 | −175.6 (4) | C43—C41—C42—N8 | 155.2 (4) |
N3—C11—C12—O3 | 163.1 (4) | N7—C41—C43—C44 | 56.3 (6) |
C13—C11—C12—O3 | −72.6 (5) | C42—C41—C43—C44 | −70.9 (5) |
N3—C11—C12—N4 | −19.5 (6) | N7—C41—C43—C46 | −68.2 (5) |
C13—C11—C12—N4 | 104.8 (5) | C42—C41—C43—C46 | 164.6 (4) |
N3—C11—C13—C14 | −62.6 (5) | C41—C43—C44—C45 | 164.7 (5) |
C12—C11—C13—C14 | 170.0 (4) | C46—C43—C44—C45 | −72.2 (6) |
C11—C13—C14—C19 | −64.5 (6) | C42—N8—C47—C49 | −73.9 (5) |
C11—C13—C14—C15 | 116.0 (5) | C42—N8—C47—C48 | 53.6 (5) |
C19—C14—C15—C16 | −0.7 (7) | C53—N9—C48—O8 | 0.1 (7) |
C13—C14—C15—C16 | 178.9 (4) | C53—N9—C48—C47 | 174.9 (4) |
C14—C15—C16—C17 | 1.0 (7) | N8—C47—C48—O8 | −137.5 (5) |
C15—C16—C17—C18 | −1.9 (8) | C49—C47—C48—O8 | −9.2 (6) |
C16—C17—C18—C19 | 2.6 (8) | N8—C47—C48—N9 | 47.5 (5) |
C15—C14—C19—C18 | 1.3 (7) | C49—C47—C48—N9 | 175.8 (4) |
C13—C14—C19—C18 | −178.2 (4) | N8—C47—C49—C50 | −48.7 (5) |
C17—C18—C19—C14 | −2.3 (8) | C48—C47—C49—C50 | −175.9 (4) |
C12—N4—C20—C22 | 112.4 (5) | C47—C49—C50—C51 | −55.5 (6) |
C12—N4—C20—C21 | −121.3 (4) | C47—C49—C50—C52 | −178.9 (4) |
C29—N5—C21—O4 | 7.2 (7) | C48—N9—C53—C55 | 113.3 (5) |
C29—N5—C21—C20 | −173.8 (4) | C48—N9—C53—C54 | −123.7 (5) |
N4—C20—C21—O4 | −122.1 (5) | C4—N1—C54—O9 | 6.4 (7) |
C22—C20—C21—O4 | 3.3 (6) | C1—N1—C54—O9 | 174.2 (5) |
N4—C20—C21—N5 | 58.9 (5) | C4—N1—C54—C53 | −169.4 (4) |
C22—C20—C21—N5 | −175.8 (4) | C1—N1—C54—C53 | −1.6 (7) |
N4—C20—C22—C23 | −60.5 (5) | N9—C53—C54—O9 | −88.4 (5) |
C21—C20—C22—C23 | 175.7 (4) | C55—C53—C54—O9 | 32.6 (6) |
C20—C22—C23—C24 | 96.4 (5) | N9—C53—C54—N1 | 87.5 (5) |
C20—C22—C23—C28 | −77.0 (5) | C55—C53—C54—N1 | −151.5 (4) |
C28—C23—C24—C25 | 0.0 (7) | N9—C53—C55—C57 | 169.1 (4) |
C22—C23—C24—C25 | −173.6 (4) | C54—C53—C55—C57 | 51.6 (6) |
C23—C24—C25—C26 | 0.9 (8) | N9—C53—C55—C56 | −67.9 (5) |
C24—C25—C26—C27 | −2.0 (8) | C54—C53—C55—C56 | 174.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4N···O9 | 0.88 | 2.08 | 2.834 (5) | 144 |
N7—H7···O4 | 0.88 | 2.30 | 3.112 (5) | 153 |
N8—H8···O5 | 0.88 | 2.12 | 2.985 (5) | 168 |
N9—H9N···O4 | 0.88 | 2.23 | 3.058 (5) | 157 |
N3—H3···N1S | 0.88 | 2.31 | 3.136 (7) | 157 |
C13—H13A···N1S | 0.99 | 2.67 | 3.451 (7) | 136 |
N5—H5···O8i | 0.88 | 2.60 | 3.103 (5) | 117 |
N6—H6···O8i | 0.88 | 2.42 | 3.153 (5) | 141 |
C1—H1A···O3ii | 0.99 | 2.48 | 3.378 (7) | 150 |
C31—H31B···O8i | 0.99 | 2.63 | 3.435 (6) | 139 |
C37—H37···O7i | 1.00 | 2.17 | 3.041 (6) | 145 |
C53—H53···O3ii | 1.00 | 2.35 | 3.187 (6) | 140 |
C2S—H2S1···O6iii | 0.98 | 2.37 | 3.268 (7) | 152 |
C4S—H4S1···O5 | 0.98 | 2.55 | 3.463 (9) | 155 |
C4S—H4S2···O6 | 0.98 | 2.62 | 3.246 (9) | 122 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+3/2, −y+1, z−1/2. |
Acknowledgements
The authors acknowledge the kind contribution of [1–9-NαC]-linusorb B3 from Prairie Tide Chemicals Inc. (Saskatchewan, Canada), and the assistance of Dr Youn Young Shim (University of Saskatchewan) with proof-reading this article. We are also grateful to the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Saskatchewan Ministry of Agriculture, through the Agricultural Development Fund (grant Nos. 20080205, 20120099 and 20120146), for financial support.
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