organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

(2S,3S)-2-Azaniumyl-4-[(1S,4aS,4bS,6S,7S,8aS,10aS)-6,7-dihy­dr­oxy-2,4b,8,8,10a-penta­methyl-1,4,4a,4b,5,6,7,8,8a,9,10,10a-dodeca­hydro­phenanthren-1-yl]-3-meth­­oxy­butanoate–methanol–water (1/1/1)

aInstitute of Pharmaceutical Sciences, Department of Pharmaceutial and Medicinal Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany, bDepartment of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany, and cInstitute of Pharmaceutical Sciences, Department of Pharmaceutial Biology, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany
*Correspondence e-mail: pierre.koch@uni-tuebingen.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 August 2018; accepted 23 August 2018; online 31 August 2018)

The title compound, which crystallized as a methanol and water solvate, C24H41NO5·CH4O·H2O, was obtained by heterologous expression of the brasilicardin gene cluster in the bacterium Amycolatopsis japonicum. In the crystal, the components are linked by numerous hydrogen bonds, generating a three-dimensional network.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The title compound (Fig. 1[link]), representing the aglycone of the natural products brasilicardin A and brasilicardin C, was obtained by heterologous expression of the brasilicardin gene cluster (Buchmann et al. 2016[Buchmann, A., Eitel, M., Koch, P., Schwarz, P. N., Stegmann, E., Wohlleben, W., Wolański, M., Krawiec, M., Zakrzewska-Czerwińska, J., Méndez, C., Botas, A., Núñez, L. E., Morís, F., Cortés, J. & Gross, H. (2016). Genome Announc. 4, e01391-16. doi: 10.1128/genomeA.01391-1.]) in Amycolatopsis japonicum (Schwarz et al. 2018a[Schwarz, P. N., Buchmann, A., Roller, L., Kulik, A., Gross, H., Wohlleben, W. & Stegmann, E. (2018a). Biotechnol. J. 13, 1700527.],b[Schwarz, P. N., Roller, L., Kulik, A., Wohlleben, W. & Stegmann, E. (2018b). Synth. Syst. Biotechnol. 3, 56-63.]). As a result of the antisynanti configured B ring within the perhydro­phenanthrene system, this tricyclic system is in an unusual chair–boat–chair conformation. For crystal structures of compounds having the same perhydro­phenanthrene core, see Shigemori et al. (1998[Shigemori, H., Komaki, H., Yazawa, K., Mikami, Y., Nemoto, A., Tanaka, Y., Sasaki, T., In, Y., Ishida, T. & Kobayashi, J. (1998). J. Org. Chem. 63, 6900-6904.]) and Komatsu et al. (2004[Komatsu, K., Tsuda, M., Shiro, M., Tanaka, Y., Mikami, Y. & Kobayashi, J. (2004). Bioorg. Med. Chem. 12, 5545-5551.]).

[Figure 1]
Figure 1
Mol­ecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

The crystal packing is consolidated by a three-dimensional network of numerous hydrogen bonds (Table 1[link], Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1L—H1L⋯O25 0.86 (4) 1.81 (4) 2.662 (3) 171 (4)
O1W—H1W⋯O29i 0.87 (4) 1.92 (4) 2.767 (3) 162 (4)
O1W—H2W⋯O1Lii 0.83 (4) 2.15 (4) 2.948 (3) 162 (4)
C20—H20B⋯O1W 0.99 (3) 2.47 (3) 3.423 (3) 162 (2)
C22—H22⋯O24iii 0.93 (3) 2.54 (3) 3.385 (3) 151 (3)
N26—H26A⋯O30iv 0.92 (4) 2.24 (4) 2.846 (3) 123 (3)
N26—H26B⋯O1Lv 0.92 (4) 1.95 (4) 2.869 (3) 172 (4)
N26—H26C⋯O1W 0.86 (4) 1.95 (4) 2.798 (3) 169 (3)
C28—H28A⋯O30iv 0.96 (4) 2.51 (4) 3.346 (4) 144 (3)
O29—H29⋯O25vi 0.84 (4) 1.97 (4) 2.769 (3) 157 (4)
O30—H30⋯O24vi 0.84 (4) 1.85 (4) 2.680 (3) 171 (4)
Symmetry codes: (i) [-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]; (ii) x+1, y, z; (iii) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]; (iv) [-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]; (v) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]; (vi) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].
[Figure 2]
Figure 2
Part of the crystal packing. View along the a axis. Hydrogen bonds are indicated by dashed lines.

Synthesis and crystallization

The title compound C24H41NO5 was isolated from a fermentation broth of Amycolatopsis japonicum::bcaAB01, which was cultivated under brasilicardin production conditions for 3 d (Schwarz et al. 2018a[Schwarz, P. N., Buchmann, A., Roller, L., Kulik, A., Gross, H., Wohlleben, W. & Stegmann, E. (2018a). Biotechnol. J. 13, 1700527.],b[Schwarz, P. N., Roller, L., Kulik, A., Wohlleben, W. & Stegmann, E. (2018b). Synth. Syst. Biotechnol. 3, 56-63.]). The extract was purified by flash chromatography followed by preparative HPLC to yield the product C24H41NO5 as a white solid. The solid was dissolved in a minimum of methanol and crystals suitable for X-ray determination were subsequently obtained by slow evaporation of the solvent at 298 K.

1H NMR (400 MHz, CD3OD) δ 5.30 (br s, 1H), 3.95 (d, J = 3.5 Hz, 1H), 3.75 (dd, J = 11.2, 2.9 Hz, 1H), 3.57 (ddd, J = 11.2, 9.7, 4.2 Hz, 1H), 3.45 (s, 3H), 2.85 (d, J = 9.5 Hz, 1H), 1.94–1.78 (m, 3H), 1.74–1.66 (m, 2H), 1.65 (s, 3H), 1.64–1.53 (m, 4H), 1.36–1.24 (m, 4H), 1.10 (s, 3H), 1.02 (s, 3H), 0.96 (s, 3H), 0.89 (s, 3H). 13C NMR (101 MHz, CD3OD) δ 171.5, 138.9, 123.3, 84.6, 81.2, 70.2, 57.9, 56.2, 52.5, 47.2, 45.0, 44.6, 41.0, 38.6, 37.6, 31.7, 31.2, 29.4, 29.1, 27.0, 23.1, 22.7, 18.8, 17.4. MS (ESI) calculated for C24H41NO5 (M − H) 422.3, found 422.4.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The absolute structure was indeterminate based on the present refinement. The title compound (brasilicardin aglycone) was produced by a fermentation process and we assumed that the stereochemistry of the the title compound is the same as (1) the stereochemistry of the reported natural products Brasilicardin A and Brasilicardin C (the latter one was also obtained during our fermentation process) as well as (2) the stereochemistry of the title compound reported in the proposed biosynthetic pathway scheme of Brasilicardins A and C (Hayashi et al., 2008[Hayashi, Y., Matsuura, N., Toshima, H., Itoh, N., Ishikawa, J., Mikami, Y. & Dairi, T. (2008). J. Antibiot. 61, 164, 174.]). This defines the configurations of the stereogenic centres as C2 S, C3 S, C5 S, C6 S, C7 R, C11 S, C12 S, C21, S and C22 S.

Table 2
Experimental details

Crystal data
Chemical formula C24H41NO5·CH4O·H2O
Mr 473.63
Crystal system, space group Orthorhombic, P212121
Temperature (K) 193
a, b, c (Å) 7.9093 (2), 13.3712 (4), 25.3669 (7)
V3) 2682.72 (13)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.08
Crystal size (mm) 0.45 × 0.09 × 0.08
 
Data collection
Diffractometer Stoe IPDS 2T
Absorption correction
No. of measured, independent and observed [I > 2σ(I)] reflections 17021, 6656, 5482
Rint 0.031
(sin θ/λ)max−1) 0.667
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.098, 1.07
No. of reflections 6656
No. of parameters 465
H-atom treatment Only H-atom coordinates refined
Δρmax, Δρmin (e Å−3) 0.24, −0.19
Absolute structure Flack x determined using 1941 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013)
Absolute structure parameter −0.6 (7)
Computer programs: X-AREA and X-RED (Stoe & Cie, 2011[Stoe & Cie (2011). X-RED and X-AREA. Stoe & Cie, Darmstadt, Darmstadt, Germany.]), SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]) and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Structural data


Computing details top

Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA (Stoe & Cie, 2011); data reduction: X-RED (Stoe & Cie, 2011); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015).

(2S,3S)-2-Azaniumyl-4-[(1S,4aS,4bS,6S,7S,8aS,10aS)-6,7-dihydroxy-2,4b,8,8,10a-pentamethyl-1,4,4a,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthren-1-yl]-3-methoxybutanoate–methanol–water (1/1/1) top
Crystal data top
C24H41NO5·CH4O·H2ODx = 1.173 Mg m3
Mr = 473.63Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 15328 reflections
a = 7.9093 (2) Åθ = 1.7–28.4°
b = 13.3712 (4) ŵ = 0.08 mm1
c = 25.3669 (7) ÅT = 193 K
V = 2682.72 (13) Å3Coloumn, colourless
Z = 40.45 × 0.09 × 0.08 mm
F(000) = 1040
Data collection top
Stoe IPDS 2T
diffractometer
5482 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focusRint = 0.031
Detector resolution: 6.67 pixels mm-1θmax = 28.3°, θmin = 1.7°
rotation method scansh = 109
17021 measured reflectionsk = 1717
6656 independent reflectionsl = 3327
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullOnly H-atom coordinates refined
R[F2 > 2σ(F2)] = 0.049 w = 1/[σ2(Fo2) + (0.0216P)2 + 1.5011P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098(Δ/σ)max = 0.003
S = 1.07Δρmax = 0.24 e Å3
6656 reflectionsΔρmin = 0.18 e Å3
465 parametersAbsolute structure: Flack x determined using 1941 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraintsAbsolute structure parameter: 0.6 (7)
Primary atom site location: structure-invariant direct methods
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.

Refinement. All the hydrogen atoms were localized in difference maps and their positions were refined with isotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1L0.0039 (3)0.65612 (17)0.06774 (9)0.0321 (5)
H1L0.098 (5)0.664 (3)0.0782 (15)0.040 (10)*
C2L0.0906 (5)0.5995 (3)0.10662 (15)0.0377 (8)
H2L0.209 (6)0.625 (3)0.1094 (16)0.062 (8)*
H3L0.031 (6)0.603 (3)0.1424 (17)0.062 (8)*
H4L0.099 (5)0.526 (3)0.0962 (17)0.062 (8)*
O1W0.8169 (3)0.57637 (18)0.02510 (10)0.0316 (5)
H1W0.856 (5)0.586 (3)0.0569 (16)0.046 (8)*
H2W0.879 (5)0.606 (3)0.0042 (16)0.046 (8)*
C10.2183 (4)0.3791 (3)0.29186 (11)0.0295 (7)
C20.3519 (4)0.3486 (2)0.33292 (11)0.0250 (6)
H20.383 (4)0.277 (2)0.3247 (12)0.019 (8)*
C30.5130 (4)0.4103 (2)0.32866 (11)0.0245 (6)
H30.486 (4)0.481 (2)0.3363 (12)0.021 (8)*
C40.5913 (3)0.3976 (2)0.27431 (11)0.0234 (6)
H4A0.621 (4)0.326 (3)0.2696 (13)0.027 (6)*
H4B0.701 (4)0.436 (2)0.2730 (12)0.027 (6)*
C50.4738 (3)0.4269 (2)0.22846 (11)0.0211 (6)
C60.3031 (3)0.3733 (2)0.23637 (11)0.0237 (6)
H60.331 (4)0.299 (2)0.2338 (11)0.015 (7)*
C70.5516 (3)0.3947 (2)0.17323 (10)0.0194 (5)
H70.598 (4)0.459 (2)0.1579 (11)0.015 (7)*
C80.7041 (4)0.3244 (2)0.17471 (12)0.0258 (6)
H8A0.797 (4)0.353 (2)0.1952 (13)0.030 (6)*
H8B0.678 (4)0.261 (3)0.1930 (13)0.030 (6)*
C90.7706 (4)0.3079 (2)0.11968 (12)0.0270 (6)
H90.883 (4)0.280 (2)0.1177 (13)0.030 (9)*
C100.6879 (4)0.3311 (2)0.07569 (11)0.0234 (6)
C110.5097 (3)0.3730 (2)0.07633 (10)0.0194 (5)
H110.450 (4)0.335 (2)0.0491 (12)0.020 (8)*
C120.4250 (3)0.3558 (2)0.13094 (10)0.0199 (5)
C130.2593 (3)0.4127 (2)0.13744 (11)0.0245 (6)
H13A0.182 (4)0.391 (2)0.1089 (12)0.023 (6)*
H13B0.281 (4)0.486 (2)0.1316 (12)0.023 (6)*
C140.1764 (4)0.3940 (3)0.19145 (12)0.0313 (7)
H14A0.099 (5)0.337 (3)0.1884 (15)0.042 (7)*
H14B0.101 (5)0.452 (3)0.2025 (15)0.042 (7)*
C150.1417 (5)0.4816 (3)0.30652 (15)0.0449 (10)
H15A0.230 (6)0.531 (3)0.3128 (18)0.069 (8)*
H15B0.087 (6)0.475 (3)0.3390 (19)0.069 (8)*
H15C0.064 (6)0.505 (3)0.2776 (19)0.069 (8)*
C160.0749 (4)0.3022 (3)0.29376 (14)0.0408 (9)
H16A0.028 (5)0.324 (3)0.2697 (14)0.044 (6)*
H16B0.034 (5)0.296 (3)0.3297 (16)0.044 (6)*
H16C0.123 (5)0.238 (3)0.2831 (15)0.044 (6)*
C170.4580 (5)0.5423 (2)0.22788 (14)0.0324 (7)
H17A0.571 (5)0.570 (3)0.2210 (15)0.046 (6)*
H17B0.426 (5)0.571 (3)0.2631 (16)0.046 (6)*
H17C0.375 (5)0.565 (3)0.2013 (15)0.046 (6)*
C180.7657 (4)0.3147 (3)0.02232 (14)0.0322 (7)
H18A0.694 (5)0.274 (3)0.0009 (15)0.046 (6)*
H18B0.871 (5)0.278 (3)0.0249 (15)0.046 (6)*
H18C0.784 (5)0.377 (3)0.0029 (14)0.046 (6)*
C190.3867 (4)0.2422 (2)0.13407 (13)0.0276 (6)
H19A0.302 (5)0.224 (3)0.1063 (15)0.047 (6)*
H19B0.335 (5)0.220 (3)0.1681 (16)0.047 (6)*
H19C0.482 (5)0.203 (3)0.1262 (15)0.047 (6)*
C200.5108 (3)0.4819 (2)0.05625 (11)0.0192 (5)
H20A0.522 (4)0.529 (2)0.0871 (12)0.021 (5)*
H20B0.611 (4)0.495 (2)0.0340 (12)0.021 (5)*
C210.3581 (3)0.5118 (2)0.02327 (10)0.0192 (5)
H210.256 (4)0.503 (2)0.0441 (12)0.023*
C220.3638 (3)0.6232 (2)0.00644 (10)0.0199 (5)
H220.257 (4)0.642 (2)0.0047 (11)0.021 (8)*
C230.4186 (3)0.6903 (2)0.05199 (11)0.0217 (6)
O240.5567 (2)0.73372 (15)0.04793 (8)0.0266 (5)
O250.3182 (3)0.69380 (16)0.09077 (8)0.0277 (5)
N260.4811 (3)0.6366 (2)0.03900 (9)0.0228 (5)
H26A0.441 (4)0.599 (3)0.0668 (15)0.035 (9)*
H26B0.476 (5)0.703 (3)0.0493 (15)0.048 (11)*
H26C0.583 (5)0.622 (3)0.0309 (14)0.033 (9)*
O270.3531 (3)0.44976 (14)0.02207 (8)0.0264 (5)
C280.1883 (5)0.4378 (3)0.04375 (15)0.0372 (8)
H28A0.146 (5)0.499 (3)0.0587 (15)0.043 (6)*
H28B0.114 (5)0.412 (3)0.0142 (15)0.043 (6)*
H28C0.201 (5)0.386 (3)0.0738 (15)0.043 (6)*
O290.6326 (3)0.38410 (18)0.36899 (8)0.0292 (5)
H290.644 (5)0.322 (3)0.3725 (17)0.056 (13)*
O300.2805 (3)0.35337 (18)0.38417 (8)0.0316 (5)
H300.342 (5)0.319 (3)0.4043 (16)0.050 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1L0.0246 (11)0.0397 (12)0.0319 (12)0.0017 (10)0.0002 (9)0.0074 (10)
C2L0.0330 (17)0.040 (2)0.040 (2)0.0047 (15)0.0026 (15)0.0076 (16)
O1W0.0296 (11)0.0384 (13)0.0267 (12)0.0017 (10)0.0056 (10)0.0071 (10)
C10.0246 (14)0.0452 (18)0.0187 (14)0.0086 (13)0.0035 (11)0.0082 (13)
C20.0249 (14)0.0324 (15)0.0178 (14)0.0049 (13)0.0031 (11)0.0029 (12)
C30.0286 (14)0.0285 (15)0.0163 (13)0.0032 (12)0.0034 (11)0.0003 (11)
C40.0210 (13)0.0315 (16)0.0176 (14)0.0011 (12)0.0018 (11)0.0027 (12)
C50.0213 (13)0.0258 (13)0.0163 (13)0.0027 (11)0.0028 (10)0.0031 (11)
C60.0187 (12)0.0346 (16)0.0177 (14)0.0045 (12)0.0006 (10)0.0045 (12)
C70.0182 (12)0.0241 (13)0.0158 (13)0.0006 (11)0.0003 (10)0.0022 (11)
C80.0209 (13)0.0367 (17)0.0198 (14)0.0056 (13)0.0019 (11)0.0030 (12)
C90.0216 (14)0.0329 (15)0.0265 (16)0.0068 (12)0.0043 (11)0.0007 (13)
C100.0263 (13)0.0197 (13)0.0240 (14)0.0014 (11)0.0062 (12)0.0008 (11)
C110.0216 (12)0.0219 (13)0.0146 (12)0.0006 (11)0.0012 (10)0.0009 (10)
C120.0185 (12)0.0249 (13)0.0163 (13)0.0004 (11)0.0017 (10)0.0028 (11)
C130.0185 (13)0.0378 (17)0.0173 (14)0.0009 (12)0.0006 (10)0.0048 (12)
C140.0189 (14)0.054 (2)0.0208 (15)0.0051 (15)0.0014 (11)0.0109 (14)
C150.044 (2)0.063 (2)0.0276 (18)0.031 (2)0.0105 (16)0.0109 (18)
C160.0227 (15)0.074 (3)0.0263 (17)0.0019 (17)0.0036 (13)0.0157 (18)
C170.0434 (19)0.0291 (16)0.0247 (16)0.0068 (14)0.0003 (14)0.0009 (13)
C180.0359 (17)0.0325 (17)0.0283 (17)0.0065 (14)0.0105 (14)0.0021 (14)
C190.0317 (16)0.0282 (15)0.0229 (15)0.0065 (13)0.0009 (13)0.0031 (12)
C200.0182 (12)0.0218 (12)0.0175 (13)0.0017 (10)0.0026 (10)0.0015 (11)
C210.0205 (12)0.0224 (13)0.0148 (12)0.0017 (11)0.0001 (10)0.0005 (11)
C220.0183 (12)0.0236 (13)0.0178 (13)0.0020 (11)0.0010 (10)0.0025 (11)
C230.0242 (13)0.0207 (13)0.0203 (14)0.0015 (11)0.0048 (11)0.0016 (11)
O240.0257 (10)0.0301 (10)0.0240 (11)0.0067 (9)0.0000 (8)0.0047 (8)
O250.0282 (10)0.0318 (11)0.0232 (11)0.0027 (9)0.0044 (9)0.0040 (8)
N260.0232 (12)0.0285 (13)0.0167 (12)0.0027 (11)0.0029 (9)0.0016 (10)
O270.0302 (10)0.0275 (10)0.0214 (10)0.0017 (9)0.0068 (9)0.0045 (8)
C280.0405 (18)0.0313 (17)0.040 (2)0.0045 (15)0.0196 (16)0.0011 (15)
O290.0352 (12)0.0338 (12)0.0187 (10)0.0026 (10)0.0071 (9)0.0021 (9)
O300.0310 (11)0.0463 (13)0.0174 (10)0.0134 (10)0.0049 (9)0.0091 (10)
Geometric parameters (Å, º) top
O1L—C2L1.420 (4)C13—C141.539 (4)
O1L—H1L0.86 (4)C13—H13A0.99 (3)
C2L—H2L1.00 (4)C13—H13B1.01 (3)
C2L—H3L1.02 (4)C14—H14A0.99 (4)
C2L—H4L1.02 (5)C14—H14B1.02 (4)
O1W—H1W0.87 (4)C15—H15A0.97 (5)
O1W—H2W0.83 (4)C15—H15B0.94 (5)
C1—C161.531 (5)C15—H15C1.00 (5)
C1—C21.539 (4)C16—H16A1.06 (4)
C1—C151.544 (5)C16—H16B0.97 (4)
C1—C61.561 (4)C16—H16C0.98 (4)
C2—O301.419 (3)C17—H17A0.99 (4)
C2—C31.522 (4)C17—H17B1.00 (4)
C2—H21.01 (3)C17—H17C0.99 (4)
C3—O291.436 (3)C18—H18A0.98 (4)
C3—C41.521 (4)C18—H18B0.97 (4)
C3—H30.99 (3)C18—H18C0.98 (4)
C4—C51.539 (4)C19—H19A1.00 (4)
C4—H4A0.99 (3)C19—H19B1.00 (4)
C4—H4B1.00 (3)C19—H19C0.94 (4)
C5—C61.542 (4)C20—C211.523 (4)
C5—C171.549 (4)C20—H20A1.01 (3)
C5—C71.590 (4)C20—H20B0.99 (3)
C6—C141.542 (4)C21—O271.419 (3)
C6—H61.02 (3)C21—C221.550 (4)
C7—C81.529 (4)C21—H210.97 (3)
C7—C121.557 (4)C22—N261.490 (4)
C7—H71.02 (3)C22—C231.525 (4)
C8—C91.508 (4)C22—H220.93 (3)
C8—H8A0.98 (3)C23—O241.242 (3)
C8—H8B0.98 (3)C23—O251.265 (3)
C9—C101.330 (4)N26—H26A0.92 (4)
C9—H90.96 (3)N26—H26B0.92 (4)
C10—C181.503 (4)N26—H26C0.86 (4)
C10—C111.517 (4)O27—C281.424 (4)
C11—C201.543 (4)C28—H28A0.96 (4)
C11—C121.556 (4)C28—H28B1.01 (4)
C11—H110.98 (3)C28—H28C1.04 (4)
C12—C131.524 (4)O29—H290.84 (4)
C12—C191.550 (4)O30—H300.84 (4)
C2L—O1L—H1L108 (3)C14—C13—H13A109.8 (17)
O1L—C2L—H2L109 (2)C12—C13—H13B109.1 (18)
O1L—C2L—H3L112 (2)C14—C13—H13B111.1 (18)
H2L—C2L—H3L111 (3)H13A—C13—H13B106 (2)
O1L—C2L—H4L111 (2)C13—C14—C6114.2 (2)
H2L—C2L—H4L107 (3)C13—C14—H14A109 (2)
H3L—C2L—H4L108 (3)C6—C14—H14A109 (2)
H1W—O1W—H2W108 (4)C13—C14—H14B112 (2)
C16—C1—C2108.0 (3)C6—C14—H14B108 (2)
C16—C1—C15107.3 (3)H14A—C14—H14B105 (3)
C2—C1—C15110.0 (3)C1—C15—H15A111 (3)
C16—C1—C6108.3 (3)C1—C15—H15B108 (3)
C2—C1—C6107.6 (2)H15A—C15—H15B105 (4)
C15—C1—C6115.4 (3)C1—C15—H15C109 (3)
O30—C2—C3111.9 (2)H15A—C15—H15C111 (4)
O30—C2—C1109.6 (2)H15B—C15—H15C113 (4)
C3—C2—C1112.6 (2)C1—C16—H16A112 (2)
O30—C2—H2109.1 (17)C1—C16—H16B109 (2)
C3—C2—H2107.2 (17)H16A—C16—H16B108 (3)
C1—C2—H2106.2 (17)C1—C16—H16C107 (2)
O29—C3—C4110.5 (2)H16A—C16—H16C113 (3)
O29—C3—C2111.6 (2)H16B—C16—H16C109 (3)
C4—C3—C2110.2 (2)C5—C17—H17A108 (2)
O29—C3—H3103.7 (18)C5—C17—H17B113 (2)
C4—C3—H3111.9 (17)H17A—C17—H17B104 (3)
C2—C3—H3108.8 (18)C5—C17—H17C111 (2)
C3—C4—C5114.3 (2)H17A—C17—H17C112 (3)
C3—C4—H4A108.3 (19)H17B—C17—H17C109 (3)
C5—C4—H4A107.3 (19)C10—C18—H18A113 (2)
C3—C4—H4B108.9 (18)C10—C18—H18B111 (2)
C5—C4—H4B111.6 (18)H18A—C18—H18B105 (3)
H4A—C4—H4B106 (3)C10—C18—H18C113 (2)
C4—C5—C6108.2 (2)H18A—C18—H18C105 (3)
C4—C5—C17108.0 (3)H18B—C18—H18C109 (3)
C6—C5—C17113.2 (2)C12—C19—H19A109 (2)
C4—C5—C7111.3 (2)C12—C19—H19B114 (2)
C6—C5—C7109.1 (2)H19A—C19—H19B105 (3)
C17—C5—C7107.0 (2)C12—C19—H19C112 (2)
C5—C6—C14112.9 (2)H19A—C19—H19C105 (3)
C5—C6—C1118.1 (2)H19B—C19—H19C110 (3)
C14—C6—C1112.2 (2)C21—C20—C11115.1 (2)
C5—C6—H6104.9 (16)C21—C20—H20A109.4 (17)
C14—C6—H6105.4 (16)C11—C20—H20A109.4 (17)
C1—C6—H6101.4 (16)C21—C20—H20B106.2 (17)
C8—C7—C12108.6 (2)C11—C20—H20B110.8 (17)
C8—C7—C5116.7 (2)H20A—C20—H20B105 (2)
C12—C7—C5116.6 (2)O27—C21—C20108.3 (2)
C8—C7—H7104.4 (16)O27—C21—C22109.8 (2)
C12—C7—H7104.5 (16)C20—C21—C22112.3 (2)
C5—C7—H7104.3 (16)O27—C21—H21110.3 (18)
C9—C8—C7110.0 (2)C20—C21—H21109.2 (18)
C9—C8—H8A106.7 (19)C22—C21—H21106.9 (18)
C7—C8—H8A111.4 (19)N26—C22—C23109.8 (2)
C9—C8—H8B112.6 (19)N26—C22—C21110.3 (2)
C7—C8—H8B111.8 (19)C23—C22—C21111.4 (2)
H8A—C8—H8B104 (3)N26—C22—H22107.5 (18)
C10—C9—C8124.8 (3)C23—C22—H22109.3 (19)
C10—C9—H9120 (2)C21—C22—H22108.5 (19)
C8—C9—H9115 (2)O24—C23—O25126.8 (3)
C9—C10—C18121.4 (3)O24—C23—C22117.5 (3)
C9—C10—C11122.3 (3)O25—C23—C22115.6 (2)
C18—C10—C11116.4 (3)C22—N26—H26A108 (2)
C10—C11—C20109.9 (2)C22—N26—H26B108 (3)
C10—C11—C12110.8 (2)H26A—N26—H26B106 (3)
C20—C11—C12115.9 (2)C22—N26—H26C112 (2)
C10—C11—H11104.1 (17)H26A—N26—H26C113 (3)
C20—C11—H11105.4 (17)H26B—N26—H26C109 (3)
C12—C11—H11110.0 (17)C21—O27—C28113.8 (2)
C13—C12—C19108.4 (2)O27—C28—H28A112 (2)
C13—C12—C11113.1 (2)O27—C28—H28B106 (2)
C19—C12—C11106.0 (2)H28A—C28—H28B112 (3)
C13—C12—C7108.1 (2)O27—C28—H28C106 (2)
C19—C12—C7114.7 (2)H28A—C28—H28C108 (3)
C11—C12—C7106.6 (2)H28B—C28—H28C112 (3)
C12—C13—C14112.4 (2)C3—O29—H29113 (3)
C12—C13—H13A107.9 (17)C2—O30—H30108 (3)
C16—C1—C2—O3063.7 (3)C8—C9—C10—C113.1 (5)
C15—C1—C2—O3053.2 (3)C9—C10—C11—C20113.1 (3)
C6—C1—C2—O30179.6 (3)C18—C10—C11—C2068.2 (3)
C16—C1—C2—C3171.1 (3)C9—C10—C11—C1216.2 (4)
C15—C1—C2—C372.1 (3)C18—C10—C11—C12162.5 (2)
C6—C1—C2—C354.4 (3)C10—C11—C12—C13169.4 (2)
O30—C2—C3—O2953.1 (3)C20—C11—C12—C1343.3 (3)
C1—C2—C3—O29177.1 (2)C10—C11—C12—C1972.0 (3)
O30—C2—C3—C4176.3 (2)C20—C11—C12—C19161.9 (2)
C1—C2—C3—C459.7 (3)C10—C11—C12—C750.6 (3)
O29—C3—C4—C5178.3 (2)C20—C11—C12—C775.5 (3)
C2—C3—C4—C557.8 (3)C8—C7—C12—C13168.6 (2)
C3—C4—C5—C650.5 (3)C5—C7—C12—C1334.1 (3)
C3—C4—C5—C1772.4 (3)C8—C7—C12—C1947.4 (3)
C3—C4—C5—C7170.4 (2)C5—C7—C12—C1987.0 (3)
C4—C5—C6—C14177.9 (2)C8—C7—C12—C1169.5 (3)
C17—C5—C6—C1462.4 (3)C5—C7—C12—C11156.1 (2)
C7—C5—C6—C1456.6 (3)C19—C12—C13—C1462.3 (3)
C4—C5—C6—C148.4 (3)C11—C12—C13—C14179.5 (3)
C17—C5—C6—C171.3 (3)C7—C12—C13—C1462.7 (3)
C7—C5—C6—C1169.7 (2)C12—C13—C14—C630.8 (4)
C16—C1—C6—C5167.2 (3)C5—C6—C14—C1330.5 (4)
C2—C1—C6—C550.7 (3)C1—C6—C14—C13167.0 (3)
C15—C1—C6—C572.5 (4)C10—C11—C20—C21143.4 (2)
C16—C1—C6—C1458.8 (3)C12—C11—C20—C2190.1 (3)
C2—C1—C6—C14175.3 (3)C11—C20—C21—O2760.9 (3)
C15—C1—C6—C1461.5 (4)C11—C20—C21—C22177.6 (2)
C4—C5—C7—C811.8 (3)O27—C21—C22—N2641.8 (3)
C6—C5—C7—C8107.5 (3)C20—C21—C22—N2678.8 (3)
C17—C5—C7—C8129.6 (3)O27—C21—C22—C23164.0 (2)
C4—C5—C7—C12142.5 (2)C20—C21—C22—C2343.4 (3)
C6—C5—C7—C1223.2 (3)N26—C22—C23—O248.9 (3)
C17—C5—C7—C1299.6 (3)C21—C22—C23—O24113.6 (3)
C12—C7—C8—C950.1 (3)N26—C22—C23—O25172.5 (2)
C5—C7—C8—C9175.5 (2)C21—C22—C23—O2565.0 (3)
C7—C8—C9—C1014.5 (4)C20—C21—O27—C28154.3 (2)
C8—C9—C10—C18178.3 (3)C22—C21—O27—C2882.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1L—H1L···O250.86 (4)1.81 (4)2.662 (3)171 (4)
O1W—H1W···O29i0.87 (4)1.92 (4)2.767 (3)162 (4)
O1W—H2W···O1Lii0.83 (4)2.15 (4)2.948 (3)162 (4)
C20—H20B···O1W0.99 (3)2.47 (3)3.423 (3)162 (2)
C22—H22···O24iii0.93 (3)2.54 (3)3.385 (3)151 (3)
N26—H26A···O30iv0.92 (4)2.24 (4)2.846 (3)123 (3)
N26—H26B···O1Lv0.92 (4)1.95 (4)2.869 (3)172 (4)
N26—H26C···O1W0.86 (4)1.95 (4)2.798 (3)169 (3)
C28—H28A···O30iv0.96 (4)2.51 (4)3.346 (4)144 (3)
O29—H29···O25vi0.84 (4)1.97 (4)2.769 (3)157 (4)
O30—H30···O24vi0.84 (4)1.85 (4)2.680 (3)171 (4)
Symmetry codes: (i) x+3/2, y+1, z1/2; (ii) x+1, y, z; (iii) x1/2, y+3/2, z; (iv) x+1/2, y+1, z1/2; (v) x+1/2, y+3/2, z; (vi) x+1, y1/2, z+1/2.
 

Acknowledgements

Special thanks go to all PIs and coworkers of the `NeBrasCa' consortium for helpful discussions.

Funding information

Funding for this research was provided by: Federal Ministry for Research and Education (BMBF, FKZ: 031A568A).

References

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