organic compounds
R,2R,4aS,8aS)-2-hydroxy-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]-N-(o-tolyl)acetamide
of 2-[(1aLab. for Pesticide Synthesis, Department of Pesticide Science, College of Plant Protection, Nanjing Agricultural University, Weigang 1, Xuanwu District, Nanjing 210095, People's Republic of China, and bXi'an Botanical Garden, Institute of Botany of Shaanxi Province, Xi'an 710061, People's Republic of China
*Correspondence e-mail: saintkun001@njau.edu.cn
The title compound, C23H35NO2, is an amide derivative of the lactone (+)-sclareolide, and was synthesized from natural sclareol. In the molecular structure, the two six-membered rings (A and B) of the labdane skeleton are trans-fused, and adopt chair conformations. There is an intramolecular N—H⋯O hydrogen bond present forming an S(7) ring motif. In the crystal, O—H⋯O hydrogen bonds link the molecules into helical chains propagating along the b-axis direction. The chains are linked via C—H⋯π interactions, forming a three-dimensional structure.
Keywords: crystal structure; sclareolide; sclareol; hydrogen bonding; C—H⋯π interactions.
CCDC reference: 1426216
1. Related literature
For the chemistry and biological importance of sclareol and sclareolide, see: Barrero et al. (2004); Huang et al. (2001); Mohamad et al. (2005); Sy & Brown (1997). For the synthesis of coronarin and chinensines, see: Margaros & Vassilikogiannakis (2007). For related structures, see: Bernardinelli & Giersch (1985); Shi et al. (2015).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL).
Supporting information
CCDC reference: 1426216
10.1107/S2056989015017600/su5209sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017600/su5209Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017600/su5209Isup3.cdx
The title compound, possessing an intact homodrimane skeleton, is an amide derivative of (+)-sclareolide, which was synthesized from natural sclareol (Barrero et al., 2004). The commercially available diterpene (-)-sclareol or the lactone derivative (+)-sclareolide make an ideal starting point for some biologically important natural products (Mohamad et al., 2005). Furthermore, the enantiometrically pure sclareolide provided the perfect tool to validate the absolute stereochemistry of certain chinensine family members, whose stereochemistry had been tentatively assigned based on comparisons to other biogenetically close compounds, such as coronarin E (Margaros & Vassilikogiannakis, 2007; Sy & Brown, 1997). Herein, we report on the first synthesis and
of the title compound.The molecular structure of the title compound is shown in Fig. 1. The molecule is composed of three main rings (A, B and C). The six-membered rings, A (C13/C14/C17—C20) and B (C9—C14), are trans-fused and have chair conformations. Bond angles to the aliphatic rings and to the aromatic ring C (C1—C6) are in the range of 114.40 (16) to 129.65 (16)° and 117.91 (19) to 122.2 (2)°, respectively. The methyl group at C15 and the side chain at C8 are attached in ideal equatorial positions. There is an intramolecular N—H···O hydrogen bond forming an S(7) ring motif (Table 1).
In the crystal, O—H···O hydrogen bonds link the molecules into zigzag chains propagating along the b axis direction (Table 1 and Fig. 2). The chains are linked via C—H···π interactions forming a three-dimensional structure (Table 1).
A solution of DIBAL-H (1.5 M in toluene, 2.58 ml, 3.87 mmol) was added to a cooled (273 K) solution of o-methylanilines (0.688 g, 4.0 mmol) in THF (1.7 ml) under nitrogen. The mixture was allowed to warm up and stirred at rt for 2 h. The concentration of the prepared DIBAL-H-o-CH3C6H4NH2 complex was ca 0.88 M, and was used directly for aminolysis. To a solution of (+)-sclareolide (0.168 g, 0.67 mmol) in THF (2.5 ml) was added, under nitrogen at rt, the DIBAL-H-p-C6H4NH2 complexe (3.8 ml, 3.35 mmol). After stirring at rt for 2 h, the reaction was cooled to 273 K, and then quenched with H2O (1.5 ml) and a 1 M aqueous solution of KHSO4 (4 ml). The resulting mixture was extracted with CH2Cl2 (3 × 10 ml). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The residue was purified by flash
(200-300 m ilicon) with PE/EtOAc = 6:1 as eluant to give the title compound (215 mg, yield 90 %) as a white solid (Margaros & Georgios, 2007). Colourless crystals were obtained by slow evaporation of a solution in CH2Cl2.Crystal data, data collection and structure
details are summarized in Table 2. All the H atoms could be located in difference Fourier maps. In the final cycles of they were included in calculated positions and refined as riding atoms: O—H = 0.82 Å, N—H = 0.86 Å and C—H = 0.93-0.97 Å with Uiso(H) = 1.5Ueq(C) for OH and methyl H atoms and 1.2Ueq(N,C) for other H atoms. The of the title compound is based on that of the starting reagent (+)-sclareolide.Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular N—H···O hydrogen bonds is shown as a dashed line (see Table 1). | |
Fig. 2. Crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity. |
C23H35NO2 | F(000) = 392 |
Mr = 357.52 | Dx = 1.126 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2068 reflections |
a = 6.3001 (5) Å | θ = 3.1–23.4° |
b = 13.2663 (10) Å | µ = 0.07 mm−1 |
c = 12.7082 (10) Å | T = 296 K |
β = 96.983 (2)° | Block, colorless |
V = 1054.26 (14) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 3714 independent reflections |
Radiation source: fine-focus sealed tube | 3121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
phi and ω scans | θmax = 25.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→7 |
Tmin = 0.985, Tmax = 0.987 | k = −15→14 |
3714 measured reflections | l = 0→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.0489P] where P = (Fo2 + 2Fc2)/3 |
3714 reflections | (Δ/σ)max < 0.001 |
242 parameters | Δρmax = 0.11 e Å−3 |
1 restraint | Δρmin = −0.13 e Å−3 |
C23H35NO2 | V = 1054.26 (14) Å3 |
Mr = 357.52 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.3001 (5) Å | µ = 0.07 mm−1 |
b = 13.2663 (10) Å | T = 296 K |
c = 12.7082 (10) Å | 0.22 × 0.20 × 0.18 mm |
β = 96.983 (2)° |
Bruker SMART APEX CCD diffractometer | 3714 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3121 reflections with I > 2σ(I) |
Tmin = 0.985, Tmax = 0.987 | Rint = 0.020 |
3714 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.11 e Å−3 |
3714 reflections | Δρmin = −0.13 e Å−3 |
242 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 | ||
O1 | 0.4624 (2) | 0.38763 (11) | 0.90592 (12) | 0.0598 (4) | |
H1O | 0.5362 | 0.4362 | 0.9269 | 0.090* | |
O2 | 0.3383 (3) | 0.06216 (10) | 1.00512 (14) | 0.0661 (4) | |
N1 | 0.2698 (2) | 0.22934 (12) | 1.01913 (11) | 0.0413 (4) | |
H1 | 0.3134 | 0.2876 | 1.0012 | 0.050* | |
C1 | 0.0998 (3) | 0.23103 (14) | 1.08233 (13) | 0.0373 (4) | |
C2 | 0.0322 (3) | 0.32517 (14) | 1.11475 (15) | 0.0449 (5) | |
C3 | −0.1453 (4) | 0.32833 (19) | 1.16972 (18) | 0.0601 (6) | |
H3 | −0.1947 | 0.3906 | 1.1900 | 0.072* | |
C4 | −0.2502 (4) | 0.2428 (2) | 1.19504 (17) | 0.0647 (6) | |
H4 | −0.3692 | 0.2472 | 1.2315 | 0.078* | |
C5 | −0.1783 (4) | 0.1515 (2) | 1.16623 (18) | 0.0608 (6) | |
H5 | −0.2466 | 0.0931 | 1.1848 | 0.073* | |
C6 | −0.0049 (3) | 0.14439 (16) | 1.10965 (17) | 0.0503 (5) | |
H6 | 0.0419 | 0.0815 | 1.0898 | 0.060* | |
C7 | 0.3739 (3) | 0.15013 (14) | 0.98281 (15) | 0.0412 (4) | |
C8 | 0.5396 (3) | 0.17800 (15) | 0.91191 (16) | 0.0448 (5) | |
H8A | 0.6079 | 0.1167 | 0.8914 | 0.054* | |
H8B | 0.6485 | 0.2187 | 0.9523 | 0.054* | |
C9 | 0.4531 (3) | 0.23662 (13) | 0.80977 (13) | 0.0351 (4) | |
H9 | 0.2994 | 0.2439 | 0.8135 | 0.042* | |
C10 | 0.5404 (3) | 0.34563 (14) | 0.81224 (16) | 0.0461 (5) | |
C11 | 0.4370 (4) | 0.40191 (15) | 0.71547 (18) | 0.0601 (6) | |
H11A | 0.5034 | 0.4677 | 0.7131 | 0.072* | |
H11B | 0.2869 | 0.4123 | 0.7224 | 0.072* | |
C12 | 0.4552 (4) | 0.34729 (15) | 0.61180 (17) | 0.0584 (6) | |
H12A | 0.6046 | 0.3408 | 0.6016 | 0.070* | |
H12B | 0.3838 | 0.3862 | 0.5532 | 0.070* | |
C13 | 0.3536 (3) | 0.24265 (16) | 0.61310 (15) | 0.0458 (5) | |
H13 | 0.2113 | 0.2551 | 0.6342 | 0.055* | |
C14 | 0.4691 (3) | 0.17743 (14) | 0.70513 (14) | 0.0380 (4) | |
C15 | 0.7835 (4) | 0.35592 (19) | 0.82392 (19) | 0.0667 (7) | |
H15A | 0.8226 | 0.4244 | 0.8415 | 0.100* | |
H15B | 0.8349 | 0.3379 | 0.7584 | 0.100* | |
H15C | 0.8459 | 0.3120 | 0.8793 | 0.100* | |
C16 | 0.7032 (3) | 0.15146 (18) | 0.69257 (18) | 0.0558 (5) | |
H16A | 0.7818 | 0.1407 | 0.7612 | 0.084* | |
H16B | 0.7663 | 0.2061 | 0.6578 | 0.084* | |
H16C | 0.7073 | 0.0913 | 0.6508 | 0.084* | |
C17 | 0.3428 (3) | 0.07858 (15) | 0.71010 (17) | 0.0507 (5) | |
H17A | 0.4192 | 0.0347 | 0.7628 | 0.061* | |
H17B | 0.2047 | 0.0936 | 0.7329 | 0.061* | |
C18 | 0.3081 (5) | 0.02307 (19) | 0.6044 (2) | 0.0782 (8) | |
H18A | 0.4451 | 0.0016 | 0.5847 | 0.094* | |
H18B | 0.2220 | −0.0366 | 0.6116 | 0.094* | |
C19 | 0.1974 (4) | 0.0897 (2) | 0.5183 (2) | 0.0848 (9) | |
H19A | 0.0535 | 0.1032 | 0.5343 | 0.102* | |
H19B | 0.1858 | 0.0530 | 0.4518 | 0.102* | |
C20 | 0.3085 (4) | 0.1906 (2) | 0.50341 (17) | 0.0658 (6) | |
C21 | 0.5087 (5) | 0.1731 (3) | 0.4470 (2) | 0.0896 (9) | |
H21A | 0.6003 | 0.1248 | 0.4861 | 0.134* | |
H21B | 0.5843 | 0.2356 | 0.4431 | 0.134* | |
H21C | 0.4663 | 0.1482 | 0.3767 | 0.134* | |
C22 | 0.1549 (6) | 0.2562 (3) | 0.4303 (2) | 0.1163 (13) | |
H22A | 0.1083 | 0.2197 | 0.3664 | 0.174* | |
H22B | 0.2268 | 0.3167 | 0.4131 | 0.174* | |
H22C | 0.0333 | 0.2732 | 0.4655 | 0.174* | |
C23 | 0.1454 (4) | 0.42079 (16) | 1.0915 (2) | 0.0669 (7) | |
H23A | 0.0722 | 0.4774 | 1.1175 | 0.100* | |
H23B | 0.1467 | 0.4273 | 1.0164 | 0.100* | |
H23C | 0.2897 | 0.4188 | 1.1259 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0856 (11) | 0.0399 (8) | 0.0583 (9) | −0.0191 (7) | 0.0266 (8) | −0.0166 (7) |
O2 | 0.0854 (11) | 0.0327 (8) | 0.0842 (11) | 0.0119 (8) | 0.0266 (9) | 0.0162 (8) |
N1 | 0.0510 (9) | 0.0274 (8) | 0.0467 (9) | −0.0027 (7) | 0.0110 (7) | 0.0035 (7) |
C1 | 0.0414 (9) | 0.0384 (10) | 0.0314 (9) | −0.0004 (9) | 0.0012 (7) | 0.0030 (8) |
C2 | 0.0536 (12) | 0.0420 (11) | 0.0392 (11) | 0.0005 (9) | 0.0056 (9) | −0.0023 (8) |
C3 | 0.0650 (14) | 0.0676 (16) | 0.0497 (13) | 0.0086 (13) | 0.0145 (11) | −0.0088 (11) |
C4 | 0.0582 (13) | 0.092 (2) | 0.0467 (13) | 0.0002 (14) | 0.0160 (10) | 0.0072 (13) |
C5 | 0.0603 (13) | 0.0724 (16) | 0.0495 (13) | −0.0172 (12) | 0.0059 (11) | 0.0188 (12) |
C6 | 0.0605 (13) | 0.0429 (11) | 0.0473 (12) | −0.0045 (10) | 0.0051 (10) | 0.0092 (9) |
C7 | 0.0497 (11) | 0.0344 (11) | 0.0379 (10) | 0.0053 (9) | −0.0009 (8) | 0.0056 (8) |
C8 | 0.0452 (11) | 0.0438 (11) | 0.0449 (11) | 0.0107 (9) | 0.0044 (8) | −0.0001 (9) |
C9 | 0.0365 (9) | 0.0314 (9) | 0.0383 (10) | 0.0025 (8) | 0.0075 (7) | 0.0001 (8) |
C10 | 0.0594 (12) | 0.0352 (11) | 0.0459 (12) | −0.0093 (9) | 0.0151 (9) | −0.0071 (8) |
C11 | 0.0855 (16) | 0.0337 (12) | 0.0642 (15) | −0.0013 (11) | 0.0215 (12) | 0.0091 (10) |
C12 | 0.0787 (15) | 0.0495 (13) | 0.0489 (13) | 0.0011 (11) | 0.0152 (11) | 0.0159 (10) |
C13 | 0.0433 (10) | 0.0532 (12) | 0.0415 (11) | 0.0001 (9) | 0.0079 (8) | 0.0025 (9) |
C14 | 0.0395 (10) | 0.0366 (10) | 0.0397 (10) | −0.0017 (8) | 0.0116 (8) | −0.0019 (7) |
C15 | 0.0656 (14) | 0.0696 (16) | 0.0664 (15) | −0.0320 (12) | 0.0143 (11) | −0.0156 (12) |
C16 | 0.0493 (12) | 0.0572 (13) | 0.0639 (14) | 0.0062 (10) | 0.0193 (10) | −0.0053 (11) |
C17 | 0.0610 (13) | 0.0417 (12) | 0.0520 (13) | −0.0102 (10) | 0.0172 (10) | −0.0090 (9) |
C18 | 0.104 (2) | 0.0623 (17) | 0.0738 (19) | −0.0359 (15) | 0.0339 (16) | −0.0293 (13) |
C19 | 0.0888 (19) | 0.111 (2) | 0.0561 (17) | −0.0440 (17) | 0.0149 (14) | −0.0369 (16) |
C20 | 0.0702 (14) | 0.0887 (18) | 0.0385 (12) | −0.0182 (13) | 0.0066 (11) | −0.0055 (11) |
C21 | 0.106 (2) | 0.117 (2) | 0.0529 (16) | −0.0345 (18) | 0.0368 (15) | −0.0212 (15) |
C22 | 0.117 (3) | 0.166 (4) | 0.0575 (17) | −0.009 (2) | −0.0239 (17) | 0.0145 (19) |
C23 | 0.0797 (16) | 0.0373 (12) | 0.0870 (18) | −0.0010 (11) | 0.0236 (14) | −0.0140 (11) |
O1—C10 | 1.453 (2) | C13—C20 | 1.551 (3) |
O1—H1O | 0.8200 | C13—C14 | 1.562 (3) |
O2—C7 | 1.228 (2) | C13—H13 | 0.9800 |
N1—C7 | 1.349 (2) | C14—C17 | 1.539 (3) |
N1—C1 | 1.415 (2) | C14—C16 | 1.541 (3) |
N1—H1 | 0.8600 | C15—H15A | 0.9600 |
C1—C6 | 1.390 (3) | C15—H15B | 0.9600 |
C1—C2 | 1.398 (3) | C15—H15C | 0.9600 |
C2—C3 | 1.390 (3) | C16—H16A | 0.9600 |
C2—C23 | 1.502 (3) | C16—H16B | 0.9600 |
C3—C4 | 1.371 (3) | C16—H16C | 0.9600 |
C3—H3 | 0.9300 | C17—C18 | 1.524 (3) |
C4—C5 | 1.358 (4) | C17—H17A | 0.9700 |
C4—H4 | 0.9300 | C17—H17B | 0.9700 |
C5—C6 | 1.382 (3) | C18—C19 | 1.510 (4) |
C5—H5 | 0.9300 | C18—H18A | 0.9700 |
C6—H6 | 0.9300 | C18—H18B | 0.9700 |
C7—C8 | 1.506 (3) | C19—C20 | 1.533 (4) |
C8—C9 | 1.554 (3) | C19—H19A | 0.9700 |
C8—H8A | 0.9700 | C19—H19B | 0.9700 |
C8—H8B | 0.9700 | C20—C22 | 1.529 (4) |
C9—C10 | 1.546 (3) | C20—C21 | 1.542 (4) |
C9—C14 | 1.558 (2) | C21—H21A | 0.9600 |
C9—H9 | 0.9800 | C21—H21B | 0.9600 |
C10—C11 | 1.516 (3) | C21—H21C | 0.9600 |
C10—C15 | 1.527 (3) | C22—H22A | 0.9600 |
C11—C12 | 1.520 (3) | C22—H22B | 0.9600 |
C11—H11A | 0.9700 | C22—H22C | 0.9600 |
C11—H11B | 0.9700 | C23—H23A | 0.9600 |
C12—C13 | 1.530 (3) | C23—H23B | 0.9600 |
C12—H12A | 0.9700 | C23—H23C | 0.9600 |
C12—H12B | 0.9700 | ||
C10—O1—H1O | 109.5 | C17—C14—C16 | 108.65 (16) |
C7—N1—C1 | 129.73 (16) | C17—C14—C9 | 107.87 (14) |
C7—N1—H1 | 115.1 | C16—C14—C9 | 111.29 (15) |
C1—N1—H1 | 115.1 | C17—C14—C13 | 107.85 (15) |
C6—C1—C2 | 119.63 (17) | C16—C14—C13 | 114.27 (15) |
C6—C1—N1 | 122.93 (18) | C9—C14—C13 | 106.69 (14) |
C2—C1—N1 | 117.40 (16) | C10—C15—H15A | 109.5 |
C3—C2—C1 | 117.90 (19) | C10—C15—H15B | 109.5 |
C3—C2—C23 | 120.25 (19) | H15A—C15—H15B | 109.5 |
C1—C2—C23 | 121.85 (18) | C10—C15—H15C | 109.5 |
C4—C3—C2 | 122.2 (2) | H15A—C15—H15C | 109.5 |
C4—C3—H3 | 118.9 | H15B—C15—H15C | 109.5 |
C2—C3—H3 | 118.9 | C14—C16—H16A | 109.5 |
C5—C4—C3 | 119.3 (2) | C14—C16—H16B | 109.5 |
C5—C4—H4 | 120.4 | H16A—C16—H16B | 109.5 |
C3—C4—H4 | 120.4 | C14—C16—H16C | 109.5 |
C4—C5—C6 | 120.8 (2) | H16A—C16—H16C | 109.5 |
C4—C5—H5 | 119.6 | H16B—C16—H16C | 109.5 |
C6—C5—H5 | 119.6 | C18—C17—C14 | 113.26 (17) |
C5—C6—C1 | 120.2 (2) | C18—C17—H17A | 108.9 |
C5—C6—H6 | 119.9 | C14—C17—H17A | 108.9 |
C1—C6—H6 | 119.9 | C18—C17—H17B | 108.9 |
O2—C7—N1 | 123.46 (17) | C14—C17—H17B | 108.9 |
O2—C7—C8 | 122.06 (17) | H17A—C17—H17B | 107.7 |
N1—C7—C8 | 114.48 (16) | C19—C18—C17 | 111.1 (2) |
C7—C8—C9 | 115.10 (15) | C19—C18—H18A | 109.4 |
C7—C8—H8A | 108.5 | C17—C18—H18A | 109.4 |
C9—C8—H8A | 108.5 | C19—C18—H18B | 109.4 |
C7—C8—H8B | 108.5 | C17—C18—H18B | 109.4 |
C9—C8—H8B | 108.5 | H18A—C18—H18B | 108.0 |
H8A—C8—H8B | 107.5 | C18—C19—C20 | 115.0 (2) |
C10—C9—C8 | 111.30 (15) | C18—C19—H19A | 108.5 |
C10—C9—C14 | 115.40 (14) | C20—C19—H19A | 108.5 |
C8—C9—C14 | 114.09 (15) | C18—C19—H19B | 108.5 |
C10—C9—H9 | 104.9 | C20—C19—H19B | 108.5 |
C8—C9—H9 | 104.9 | H19A—C19—H19B | 107.5 |
C14—C9—H9 | 104.9 | C22—C20—C19 | 107.9 (2) |
O1—C10—C11 | 108.73 (17) | C22—C20—C21 | 107.2 (2) |
O1—C10—C15 | 108.72 (17) | C19—C20—C21 | 109.7 (2) |
C11—C10—C15 | 111.21 (18) | C22—C20—C13 | 109.0 (2) |
O1—C10—C9 | 102.74 (14) | C19—C20—C13 | 108.33 (18) |
C11—C10—C9 | 109.11 (16) | C21—C20—C13 | 114.47 (19) |
C15—C10—C9 | 115.82 (17) | C20—C21—H21A | 109.5 |
C10—C11—C12 | 113.45 (17) | C20—C21—H21B | 109.5 |
C10—C11—H11A | 108.9 | H21A—C21—H21B | 109.5 |
C12—C11—H11A | 108.9 | C20—C21—H21C | 109.5 |
C10—C11—H11B | 108.9 | H21A—C21—H21C | 109.5 |
C12—C11—H11B | 108.9 | H21B—C21—H21C | 109.5 |
H11A—C11—H11B | 107.7 | C20—C22—H22A | 109.5 |
C11—C12—C13 | 110.33 (17) | C20—C22—H22B | 109.5 |
C11—C12—H12A | 109.6 | H22A—C22—H22B | 109.5 |
C13—C12—H12A | 109.6 | C20—C22—H22C | 109.5 |
C11—C12—H12B | 109.6 | H22A—C22—H22C | 109.5 |
C13—C12—H12B | 109.6 | H22B—C22—H22C | 109.5 |
H12A—C12—H12B | 108.1 | C2—C23—H23A | 109.5 |
C12—C13—C20 | 115.19 (17) | C2—C23—H23B | 109.5 |
C12—C13—C14 | 110.69 (16) | H23A—C23—H23B | 109.5 |
C20—C13—C14 | 116.36 (18) | C2—C23—H23C | 109.5 |
C12—C13—H13 | 104.3 | H23A—C23—H23C | 109.5 |
C20—C13—H13 | 104.3 | H23B—C23—H23C | 109.5 |
C14—C13—H13 | 104.3 | ||
C7—N1—C1—C6 | −6.7 (3) | C11—C12—C13—C20 | 164.77 (19) |
C7—N1—C1—C2 | 175.54 (18) | C11—C12—C13—C14 | −60.6 (2) |
C6—C1—C2—C3 | −2.8 (3) | C10—C9—C14—C17 | −170.84 (16) |
N1—C1—C2—C3 | 175.04 (18) | C8—C9—C14—C17 | 58.41 (19) |
C6—C1—C2—C23 | 177.3 (2) | C10—C9—C14—C16 | 70.1 (2) |
N1—C1—C2—C23 | −4.9 (3) | C8—C9—C14—C16 | −60.7 (2) |
C1—C2—C3—C4 | 1.8 (3) | C10—C9—C14—C13 | −55.19 (19) |
C23—C2—C3—C4 | −178.3 (2) | C8—C9—C14—C13 | 174.06 (14) |
C2—C3—C4—C5 | 0.4 (3) | C12—C13—C14—C17 | 173.35 (16) |
C3—C4—C5—C6 | −1.7 (3) | C20—C13—C14—C17 | −52.6 (2) |
C4—C5—C6—C1 | 0.6 (3) | C12—C13—C14—C16 | −65.7 (2) |
C2—C1—C6—C5 | 1.7 (3) | C20—C13—C14—C16 | 68.3 (2) |
N1—C1—C6—C5 | −176.07 (18) | C12—C13—C14—C9 | 57.69 (19) |
C1—N1—C7—O2 | −3.4 (3) | C20—C13—C14—C9 | −168.28 (15) |
C1—N1—C7—C8 | 176.65 (17) | C16—C14—C17—C18 | −70.6 (2) |
O2—C7—C8—C9 | 120.4 (2) | C9—C14—C17—C18 | 168.6 (2) |
N1—C7—C8—C9 | −59.7 (2) | C13—C14—C17—C18 | 53.7 (2) |
C7—C8—C9—C10 | 113.33 (18) | C14—C17—C18—C19 | −56.3 (3) |
C7—C8—C9—C14 | −113.93 (17) | C17—C18—C19—C20 | 55.1 (3) |
C8—C9—C10—O1 | −60.06 (18) | C18—C19—C20—C22 | −168.8 (2) |
C14—C9—C10—O1 | 167.86 (14) | C18—C19—C20—C21 | 74.7 (3) |
C8—C9—C10—C11 | −175.33 (16) | C18—C19—C20—C13 | −51.0 (3) |
C14—C9—C10—C11 | 52.6 (2) | C12—C13—C20—C22 | −60.1 (3) |
C8—C9—C10—C15 | 58.3 (2) | C14—C13—C20—C22 | 168.0 (2) |
C14—C9—C10—C15 | −73.8 (2) | C12—C13—C20—C19 | −177.2 (2) |
O1—C10—C11—C12 | −163.68 (17) | C14—C13—C20—C19 | 50.8 (3) |
C15—C10—C11—C12 | 76.6 (2) | C12—C13—C20—C21 | 60.0 (3) |
C9—C10—C11—C12 | −52.3 (2) | C14—C13—C20—C21 | −72.0 (3) |
C10—C11—C12—C13 | 58.1 (3) |
Cg is the centroid of benzene ring C1–C6. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 2.09 | 2.894 (2) | 155 |
O1—H1O···O2i | 0.82 | 2.00 | 2.8054 (19) | 168 |
C8—H8B···Cgii | 0.97 | 2.79 | 3.632 (2) | 146 |
C22—H22A···Cgiii | 0.96 | 2.98 | 3.808 (3) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x+1, y, z; (iii) x, y, z−1. |
Cg is the centroid of benzene ring C1–C6. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 2.09 | 2.894 (2) | 155 |
O1—H1O···O2i | 0.82 | 2.00 | 2.8054 (19) | 168 |
C8—H8B···Cgii | 0.97 | 2.79 | 3.632 (2) | 146 |
C22—H22A···Cgiii | 0.96 | 2.98 | 3.808 (3) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x+1, y, z; (iii) x, y, z−1. |
Acknowledgements
This project was supported by the National Natural Science Foundation of China (Nos. 3140177 and 31200257), the Science and Technology Research and Development Projects of Shaanxi Province (No. 2013KJXX-74) and the National Science Foundation of Jiangsu Province (No. BK20140684).
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