research communications
and Hirshfeld surface analysis of pulcherrin J
aDepartment of Chemistry, Faculty of Physical Sciences, University of Benin, Benin City, Nigeria, bH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, cDepartment of Chemistry, School of Sciences, The Federal University of Technology, Akure, Nigeria, and dDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, University of Benin, Benin City, Nigeria
*Correspondence e-mail: dr.sammer.yousuf@gmail.com
The title compound, C29H36O4 [systematic name (4aR,5R,6aS,7R,11aS,11bR)-4a-hydroxy-4,4,7,11b-tetramethyl-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydrophenanthro[3,2-b]furan-5-yl cinnamate], a natural diterpene known as pulcherrin J, was isolated from stem barks of medicinally important Caesalpinia pulcherrima (L.). The of pulcherrin J shows it to be composed of a central core of three trans-fused cyclohexane rings and a near planar five-membered furan ring, along with an axially oriented cinnamate moiety and an hydroxy substituent attached at positions 4a and 5 of the steroid ring system, respectively. The was established with the use of Cu Kα radiation. In the crystal, molecules are linked by O—H⋯O hydrogen bonds to generate [100] C(8) chains. Hirshfeld surface analysis indicates that the most significant contacts in packing are H⋯H (67.5%), followed by C⋯H (19.6%) and H⋯O (12.9%).
Keywords: crystal structure; Pulcherrin J; Caesalpinia pulcherrima (L.); diterpene; Hirshfeld surface analysis.
CCDC reference: 1565682
1. Chemical context
Caesalpinia pulcherrima (L.) is one of the widely cultivated species of the genus Caesalpinia. It is an ornamental plant with attractive inflorescence in yellow, red, and orange, generally blooming in winter. Its small size and tolerability towards pruning allows it to be grown in groups to form a windbreak. It can also be used to create a center of attention for humming birds (Frisch et al., 2005). In addition to the ornamental value, C. pulcherrima has been known to exhibit cytotoxic (Promsawan et al., 2003; McPherson et al., 1986), antitubercular (Promsawan et al., 2003), antibacterial, antifungal (Ragasa et al., 2002), and leishmanicidal (Erharuyi et al., 2016) activities. The compounds isolated from C. pulcherrima are also reported to be active against DNA repair-deficient yeast mutant (Patil et al., 1997). The plants of genus Caesalpinia, including C. pulcherrima, are known to be a rich source of cassane-type The literature reports the isolation of a number of cassane-type from the stems, and root barks, such as pulcherrimins A–F, and pulcherrins A–R (Erharuyi et al., 2017; Yodsaoue et al., 2011; Pranithanchai et al., 2009; Roach et al., 2003). In continuation of our work on the phytochemical investigation of medicinally important plants, we have isolated the crystalline pulcherrin J, a cassane-type diterpenoid, previously reported by Erharuyi and co-workers (Erharuyi et al., 2017). To the best of our knowledge, this is the first report of the the and the Hirshfeld surface analysis of pulcherrin J.
2. Structural commentary
The title compound (Fig. 1) is a cassane-type diterpenoid comprising of three cyclohexane rings A (C1–C3/C5–C7), B (C6–C11) and C (C9–10/C12–C15) and an almost planar five-membered furan ring (O1/C2–C3/C20–C21) fused to ring A along the C2—C3 bond. Cyclohexane rings A, B, and C are trans fused to each other along the C6—C11 and C8—C9 bonds and attain half-chair, chair and chair conformations, respectively, as observed in related structures (Gómez-Hurtado et al., 2013; Fun et al., 2010a,b; Matsuno et al., 2008; Ruggiero et al., 1997). The axially oriented cinnamate group (O3/O4/C22–C30) and hydroxy moieties at C8 and C9 of ring B, respectively, are trans to each other [O2—C9—C8—O3 = −171.41 (13)°]. The dihedral angle between the furan and phenyl ring of the cinnamate moiety is 83.77 (16)°. The absolute configurations of the stereogenic centres are C5 R, C6 R, C8 R, C9 R, C10 R and C11 S. The conformation of the molecule is consolidated by a C18—H18A⋯O3 intramolecular interaction, forming an S(6) graph-set ring motif.
3. Hydrogen bonding and Hirshfeld surface analysis
In the crystal, the molecules are connected by O2—H2A⋯O1i interactions to generate C(8) chains propagating in the [100] direction. (Table 1, Fig. 2). The Hirshfeld surface analysis (Spackman et al., 2009) indicates that the percentage contribution of H⋯H interactions to the packing is 67.5% (Fig. 3). Other important interactions based upon the percentages are C⋯H (19.6%) and H⋯O (12.9%), as shown in the fingerprint plots, in which cyan dots indicate the percentage of the interaction over the total Hirshfeld surface (Fig. 4).
4. Comparison with reported literature
Structurally the title compound is similar to the reported isovouacapenol C (Fun et al., 2010b) with the difference that no hydroxy substituent occurs on ring B, while the benzoate moiety is replaced by a cinnamate moiety. The O—H⋯O hydrogen bond is the most important contributor to the crystal packing of pulcherrin J, and other related structures such as isovouacapenol C and vouacapen-5a-ol (Fun et al., 2010a,b), all of which lead to chains in the crystal.
5. Isolation and crystallization
2.5 kg of ground C. pulcherrima (L.) Swartz stem bark was soaked in methanol (7.5 l) at ambient temperature: 220 g of crude extract was obtained after filtration and concentration, by using a rotary evaporator at 318 K. 200 g of the crude extract was fractionated by using silica gel first with hexane (9.4 l) followed by increasing polarities with n-hexane:ethylacetate (1:1) (12.5 l), ethyl acetate (8.2 l), ethyl acetate:methanol (1:1) (13 l) and methanol (7 l). Concentration of the different fractions in vacuo gave five different fractions of 0.45 g (0.23%), 38.81 g (19.41%), 25.75 g (12.75%), 127.73 g (63.87%) and 4.18 g (2.09%) obtained on elution with n-hexane, n-hexane:ethylacetate (1:1), ethyl acetate, ethyl acetate:methanol (1:1) and methanol, respectively. The fraction obtained on elution with n-hexane:ethyl acetate(1:1) was re-chromatographed over silica gel (SiO2, 6.5 × 135 cm column) by using increasing proportions of n-hexane with ethyl acetate [100:0 (7.5 l), 95:5 (10 l), 90:10 (24.5 l), 85:15 (7.5 l), 80:20 (6 l), and 0:100 (4.5 l)]. Each obtained fraction (250 ml of each) was monitored carefully on TLC and combined into 12 main fractions named as CP4–9, CP10–17, CP18–33, CP34–48, CP49–61, CP63–76, CP77–92, CP93–123,CP124–135, CP136–139, CP140–145 and CP153–162. The fraction obtained on elution with n-hexane:ethyl acetate 95:5 gave crystalline precipitates, which were suspended in n-hexane, filtered and dried to obtain purified crystalline pulcherrin J (130.4 mg).
1H NMR (400MHz C3D6O): 8.08 (bd, J = 7.2 H31,71), 7.64 (bt, J = 7.6, H51), 7.53 (bt, J = 7.2, Hz H41,61), 7.27 (d, J = 1.6Hz, H16), 6.20 (d, J = 2, H15), 5.6 (t, J = 3.0, H6), 2.62–2.51 (m, H9), 2.58 (m, H14), 2.46 (m, H11), 2.41–2.33 (m, H7b); 1.59–1.52 (m H7a), 2.13–2.07 (m, H8), 1.56 (s, H20), 1.21 (s, H19), 1.03 (s, H18), 0.98 (d, J = 6.8 Hz, H17), 1.98–1.89 (m, H3b); 1.05 (m, H3a), 1.79–1.77 (m, H2b); 1.49–1.47 (m, H2a), 1.76–1.74 (m, H1b); 1.45–1.43 (m, H1a) ppm. 13C NMR (400 MHz C3D6O) 165.8, 133.1, 129.7, 128.6, 149.5, 140.4, 122.4, 109.5, 76.4, 72.8, 41.3, 39.0, 38.1, 38.0, 34.9, 31.6, 31.2, 30.7, 27.8, 26.0, 21.9, 18.3, 17.6, 17.2 ppm. IR (CH3OH, cm−1): 3593.0, 2929.6, 2869.1, 1705.9, 1635.8, 1505.4, 1458.4, 1392.3, 1316.2, 1283.0, 1176.9, 1007.6, 929.7, 733.0.
6. Refinement
Crystal data, data collection and structure . H atoms were located in a difference-Fourier map, positioned with idealized geometry and refined with Uiso(H) = 1.5Ueq, C—H = 0.97 Å for CH3, 1.2Ueq, C—H = 0.97 Å for CH2 and C—H = 0.93 Å for olefinic and aromatic CH. The hydrogen atom on the oxygen [O—H= 0.82 (3) Å] was located in difference-Fourier map and refined isotropically.
details are summarized in Table 2Supporting information
CCDC reference: 1565682
https://doi.org/10.1107/S2056989017011239/hb7687sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011239/hb7687Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017011239/hb7687Isup3.cml
Data collection: SMART (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).C29H36O4 | Dx = 1.263 Mg m−3 |
Mr = 448.58 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 6933 reflections |
a = 6.6663 (3) Å | θ = 2.7–66.5° |
b = 10.6256 (5) Å | µ = 0.65 mm−1 |
c = 33.3005 (17) Å | T = 100 K |
V = 2358.8 (2) Å3 | Plate, colourless |
Z = 4 | 0.13 × 0.12 × 0.08 mm |
F(000) = 968 |
Bruker SMART APEX CCD diffractometer | 4124 independent reflections |
Radiation source: fine-focus sealed tube | 3499 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ω scans | θmax = 66.8°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −7→4 |
Tmin = 0.920, Tmax = 0.950 | k = −11→12 |
18537 measured reflections | l = −39→39 |
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.0469P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4124 reflections | Δρmax = 0.15 e Å−3 |
306 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.18 (19) |
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 | ||
O1 | 0.37182 (19) | −0.05535 (13) | 0.57637 (4) | 0.0171 (3) | |
O2 | −0.0950 (2) | −0.16046 (14) | 0.40894 (4) | 0.0144 (3) | |
O3 | 0.12570 (19) | 0.13663 (12) | 0.38017 (4) | 0.0154 (3) | |
O4 | −0.1179 (2) | 0.21242 (13) | 0.33934 (4) | 0.0201 (3) | |
C1 | 0.2954 (3) | −0.11384 (19) | 0.50647 (5) | 0.0154 (4) | |
H1A | 0.2679 | −0.2023 | 0.5140 | 0.018* | |
H1B | 0.4367 | −0.1082 | 0.4974 | 0.018* | |
C2 | 0.2654 (3) | −0.03178 (19) | 0.54176 (6) | 0.0138 (4) | |
C3 | 0.1496 (3) | 0.07066 (18) | 0.54590 (6) | 0.0140 (4) | |
C5 | 0.0101 (3) | 0.1140 (2) | 0.51340 (5) | 0.0146 (4) | |
H5 | 0.0140 | 0.2081 | 0.5128 | 0.017* | |
C6 | 0.0901 (3) | 0.06556 (18) | 0.47230 (6) | 0.0124 (4) | |
H6 | 0.2106 | 0.1170 | 0.4652 | 0.015* | |
C7 | −0.0671 (3) | 0.08691 (18) | 0.43950 (6) | 0.0142 (4) | |
H7A | −0.1916 | 0.0427 | 0.4475 | 0.017* | |
H7B | −0.0980 | 0.1780 | 0.4385 | 0.017* | |
C8 | −0.0108 (3) | 0.04400 (18) | 0.39731 (6) | 0.0131 (4) | |
H8 | −0.1356 | 0.0430 | 0.3807 | 0.016* | |
C9 | 0.0806 (3) | −0.08998 (18) | 0.39668 (5) | 0.0130 (4) | |
C10 | 0.2459 (3) | −0.10865 (19) | 0.42973 (6) | 0.0134 (4) | |
C11 | 0.1536 (3) | −0.07380 (18) | 0.47164 (5) | 0.0118 (4) | |
H11 | 0.0282 | −0.1246 | 0.4746 | 0.014* | |
C12 | 0.3090 (3) | −0.24846 (18) | 0.43029 (6) | 0.0155 (4) | |
H12A | 0.4232 | −0.2586 | 0.4490 | 0.019* | |
H12B | 0.1960 | −0.2993 | 0.4408 | 0.019* | |
C13 | 0.3700 (3) | −0.3000 (2) | 0.38903 (6) | 0.0198 (5) | |
H13A | 0.4947 | −0.2579 | 0.3801 | 0.024* | |
H13B | 0.3975 | −0.3912 | 0.3913 | 0.024* | |
C14 | 0.2051 (3) | −0.27836 (19) | 0.35786 (6) | 0.0188 (5) | |
H14A | 0.0863 | −0.3291 | 0.3654 | 0.023* | |
H14B | 0.2530 | −0.3090 | 0.3315 | 0.023* | |
C15 | 0.1407 (3) | −0.13918 (19) | 0.35356 (6) | 0.0167 (5) | |
C16 | 0.3124 (3) | −0.0690 (2) | 0.33183 (6) | 0.0242 (5) | |
H16A | 0.2714 | 0.0179 | 0.3264 | 0.036* | |
H16B | 0.3425 | −0.1115 | 0.3064 | 0.036* | |
H16C | 0.4323 | −0.0690 | 0.3489 | 0.036* | |
C17 | −0.0416 (3) | −0.1347 (2) | 0.32547 (6) | 0.0231 (5) | |
H17A | −0.1533 | −0.1808 | 0.3377 | 0.035* | |
H17B | −0.0068 | −0.1734 | 0.2997 | 0.035* | |
H17C | −0.0812 | −0.0469 | 0.3211 | 0.035* | |
C18 | 0.4348 (3) | −0.02606 (19) | 0.42266 (6) | 0.0161 (4) | |
H18A | 0.3971 | 0.0497 | 0.4077 | 0.024* | |
H18B | 0.5341 | −0.0740 | 0.4072 | 0.024* | |
H18C | 0.4925 | −0.0018 | 0.4486 | 0.024* | |
C19 | −0.2055 (3) | 0.0740 (2) | 0.52362 (6) | 0.0175 (4) | |
H19A | −0.2174 | −0.0176 | 0.5213 | 0.026* | |
H19B | −0.2990 | 0.1144 | 0.5049 | 0.026* | |
H19C | −0.2375 | 0.0998 | 0.5511 | 0.026* | |
C20 | 0.1840 (3) | 0.11595 (19) | 0.58590 (6) | 0.0172 (4) | |
H20 | 0.1234 | 0.1873 | 0.5981 | 0.021* | |
C21 | 0.3183 (3) | 0.03823 (19) | 0.60280 (6) | 0.0187 (5) | |
H21 | 0.3693 | 0.0467 | 0.6293 | 0.022* | |
C22 | 0.0525 (3) | 0.21390 (18) | 0.35149 (6) | 0.0152 (4) | |
C23 | 0.2113 (3) | 0.29919 (19) | 0.33754 (6) | 0.0169 (4) | |
H23 | 0.3381 | 0.2981 | 0.3506 | 0.020* | |
C24 | 0.1815 (3) | 0.37822 (18) | 0.30697 (6) | 0.0167 (4) | |
H24 | 0.0526 | 0.3762 | 0.2948 | 0.020* | |
C25 | 0.3260 (3) | 0.46782 (18) | 0.29013 (5) | 0.0161 (5) | |
C26 | 0.2651 (3) | 0.5491 (2) | 0.25947 (6) | 0.0215 (5) | |
H26 | 0.1334 | 0.5421 | 0.2488 | 0.026* | |
C27 | 0.3945 (4) | 0.6398 (2) | 0.24439 (6) | 0.0266 (5) | |
H27 | 0.3517 | 0.6940 | 0.2234 | 0.032* | |
C28 | 0.5861 (4) | 0.6511 (2) | 0.26003 (6) | 0.0280 (5) | |
H28 | 0.6742 | 0.7145 | 0.2503 | 0.034* | |
C29 | 0.6485 (3) | 0.5695 (2) | 0.29001 (6) | 0.0251 (5) | |
H29 | 0.7807 | 0.5765 | 0.3004 | 0.030* | |
C30 | 0.5218 (3) | 0.4784 (2) | 0.30487 (6) | 0.0216 (5) | |
H30 | 0.5675 | 0.4225 | 0.3252 | 0.026* | |
H2A | −0.075 (4) | −0.237 (3) | 0.4105 (7) | 0.036 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0206 (7) | 0.0181 (8) | 0.0127 (7) | −0.0011 (6) | −0.0039 (6) | 0.0009 (6) |
O2 | 0.0138 (7) | 0.0121 (8) | 0.0174 (7) | −0.0050 (6) | −0.0006 (5) | 0.0018 (6) |
O3 | 0.0167 (7) | 0.0145 (8) | 0.0151 (7) | −0.0016 (6) | −0.0021 (6) | 0.0062 (6) |
O4 | 0.0215 (8) | 0.0202 (8) | 0.0187 (7) | −0.0006 (6) | −0.0053 (6) | 0.0057 (6) |
C1 | 0.0169 (10) | 0.0159 (11) | 0.0134 (10) | 0.0030 (9) | −0.0012 (8) | 0.0008 (8) |
C2 | 0.0160 (11) | 0.0154 (12) | 0.0101 (9) | −0.0050 (9) | −0.0021 (8) | 0.0034 (8) |
C3 | 0.0175 (11) | 0.0116 (11) | 0.0128 (9) | −0.0043 (8) | 0.0022 (8) | 0.0029 (8) |
C5 | 0.0167 (10) | 0.0119 (11) | 0.0151 (10) | 0.0000 (8) | 0.0017 (8) | 0.0017 (9) |
C6 | 0.0124 (10) | 0.0103 (10) | 0.0145 (9) | −0.0023 (9) | 0.0015 (8) | 0.0042 (8) |
C7 | 0.0151 (11) | 0.0104 (11) | 0.0171 (10) | −0.0006 (9) | 0.0006 (8) | 0.0034 (8) |
C8 | 0.0129 (10) | 0.0130 (11) | 0.0134 (10) | −0.0041 (8) | −0.0018 (8) | 0.0040 (9) |
C9 | 0.0132 (10) | 0.0133 (11) | 0.0123 (10) | −0.0017 (8) | 0.0007 (8) | 0.0027 (8) |
C10 | 0.0115 (10) | 0.0143 (12) | 0.0143 (10) | 0.0000 (8) | −0.0003 (8) | 0.0014 (8) |
C11 | 0.0101 (9) | 0.0129 (10) | 0.0125 (9) | −0.0023 (8) | −0.0008 (7) | 0.0020 (8) |
C12 | 0.0130 (10) | 0.0180 (12) | 0.0154 (10) | 0.0038 (9) | −0.0021 (8) | 0.0020 (9) |
C13 | 0.0239 (12) | 0.0191 (12) | 0.0164 (10) | 0.0053 (9) | 0.0028 (8) | −0.0009 (9) |
C14 | 0.0251 (11) | 0.0189 (12) | 0.0124 (10) | 0.0011 (10) | 0.0033 (9) | −0.0027 (9) |
C15 | 0.0234 (12) | 0.0167 (12) | 0.0101 (9) | −0.0004 (9) | 0.0001 (8) | 0.0004 (9) |
C16 | 0.0350 (13) | 0.0240 (13) | 0.0135 (10) | −0.0009 (11) | 0.0067 (9) | 0.0002 (9) |
C17 | 0.0342 (13) | 0.0211 (13) | 0.0140 (10) | 0.0024 (10) | −0.0052 (9) | −0.0005 (10) |
C18 | 0.0118 (10) | 0.0200 (12) | 0.0166 (10) | −0.0004 (8) | −0.0002 (8) | −0.0011 (9) |
C19 | 0.0179 (10) | 0.0187 (12) | 0.0159 (10) | 0.0020 (9) | 0.0034 (9) | 0.0011 (9) |
C20 | 0.0214 (11) | 0.0167 (11) | 0.0134 (9) | −0.0028 (9) | 0.0035 (8) | 0.0005 (8) |
C21 | 0.0252 (12) | 0.0211 (12) | 0.0097 (9) | −0.0069 (10) | 0.0004 (9) | −0.0026 (9) |
C22 | 0.0240 (12) | 0.0118 (11) | 0.0097 (9) | 0.0041 (9) | −0.0005 (8) | −0.0006 (8) |
C23 | 0.0213 (11) | 0.0158 (11) | 0.0136 (9) | −0.0021 (9) | −0.0010 (8) | 0.0017 (9) |
C24 | 0.0235 (11) | 0.0153 (11) | 0.0113 (9) | 0.0006 (9) | 0.0008 (9) | −0.0038 (8) |
C25 | 0.0294 (12) | 0.0101 (11) | 0.0086 (9) | 0.0003 (9) | 0.0020 (9) | −0.0012 (8) |
C26 | 0.0337 (13) | 0.0183 (13) | 0.0126 (10) | 0.0008 (10) | −0.0040 (9) | −0.0009 (9) |
C27 | 0.0472 (15) | 0.0196 (12) | 0.0132 (10) | −0.0034 (12) | −0.0014 (10) | 0.0054 (9) |
C28 | 0.0395 (14) | 0.0236 (13) | 0.0208 (11) | −0.0101 (11) | 0.0070 (10) | 0.0051 (10) |
C29 | 0.0314 (13) | 0.0258 (13) | 0.0181 (11) | −0.0052 (10) | 0.0017 (9) | 0.0025 (10) |
C30 | 0.0296 (13) | 0.0190 (12) | 0.0163 (10) | −0.0002 (9) | 0.0000 (10) | 0.0037 (9) |
O1—C21 | 1.375 (2) | C14—C15 | 1.547 (3) |
O1—C2 | 1.376 (2) | C14—H14A | 0.9900 |
O2—C9 | 1.448 (2) | C14—H14B | 0.9900 |
O2—H2A | 0.82 (3) | C15—C17 | 1.534 (3) |
O3—C22 | 1.351 (2) | C15—C16 | 1.546 (3) |
O3—C8 | 1.457 (2) | C16—H16A | 0.9800 |
O4—C22 | 1.206 (2) | C16—H16B | 0.9800 |
C1—C2 | 1.477 (3) | C16—H16C | 0.9800 |
C1—C11 | 1.556 (3) | C17—H17A | 0.9800 |
C1—H1A | 0.9900 | C17—H17B | 0.9800 |
C1—H1B | 0.9900 | C17—H17C | 0.9800 |
C2—C3 | 1.342 (3) | C18—H18A | 0.9800 |
C3—C20 | 1.435 (3) | C18—H18B | 0.9800 |
C3—C5 | 1.499 (3) | C18—H18C | 0.9800 |
C5—C19 | 1.537 (3) | C19—H19A | 0.9800 |
C5—C6 | 1.556 (3) | C19—H19B | 0.9800 |
C5—H5 | 1.0000 | C19—H19C | 0.9800 |
C6—C7 | 1.530 (3) | C20—C21 | 1.342 (3) |
C6—C11 | 1.540 (3) | C20—H20 | 0.9500 |
C6—H6 | 1.0000 | C21—H21 | 0.9500 |
C7—C8 | 1.524 (3) | C22—C23 | 1.469 (3) |
C7—H7A | 0.9900 | C23—C24 | 1.335 (3) |
C7—H7B | 0.9900 | C23—H23 | 0.9500 |
C8—C9 | 1.549 (3) | C24—C25 | 1.466 (3) |
C8—H8 | 1.0000 | C24—H24 | 0.9500 |
C9—C10 | 1.570 (3) | C25—C26 | 1.397 (3) |
C9—C15 | 1.580 (3) | C25—C30 | 1.399 (3) |
C10—C12 | 1.544 (3) | C26—C27 | 1.388 (3) |
C10—C18 | 1.553 (3) | C26—H26 | 0.9500 |
C10—C11 | 1.570 (3) | C27—C28 | 1.385 (3) |
C11—H11 | 1.0000 | C27—H27 | 0.9500 |
C12—C13 | 1.534 (3) | C28—C29 | 1.387 (3) |
C12—H12A | 0.9900 | C28—H28 | 0.9500 |
C12—H12B | 0.9900 | C29—C30 | 1.377 (3) |
C13—C14 | 1.529 (3) | C29—H29 | 0.9500 |
C13—H13A | 0.9900 | C30—H30 | 0.9500 |
C13—H13B | 0.9900 | ||
C21—O1—C2 | 105.71 (15) | C13—C14—C15 | 113.94 (16) |
C9—O2—H2A | 113.2 (18) | C13—C14—H14A | 108.8 |
C22—O3—C8 | 117.51 (15) | C15—C14—H14A | 108.8 |
C2—C1—C11 | 110.44 (16) | C13—C14—H14B | 108.8 |
C2—C1—H1A | 109.6 | C15—C14—H14B | 108.8 |
C11—C1—H1A | 109.6 | H14A—C14—H14B | 107.7 |
C2—C1—H1B | 109.6 | C17—C15—C16 | 106.63 (16) |
C11—C1—H1B | 109.6 | C17—C15—C14 | 107.83 (16) |
H1A—C1—H1B | 108.1 | C16—C15—C14 | 107.38 (16) |
C3—C2—O1 | 111.00 (17) | C17—C15—C9 | 110.07 (16) |
C3—C2—C1 | 129.70 (18) | C16—C15—C9 | 116.97 (17) |
O1—C2—C1 | 119.26 (17) | C14—C15—C9 | 107.63 (15) |
C2—C3—C20 | 105.98 (17) | C15—C16—H16A | 109.5 |
C2—C3—C5 | 122.13 (17) | C15—C16—H16B | 109.5 |
C20—C3—C5 | 131.80 (18) | H16A—C16—H16B | 109.5 |
C3—C5—C19 | 109.58 (15) | C15—C16—H16C | 109.5 |
C3—C5—C6 | 108.72 (15) | H16A—C16—H16C | 109.5 |
C19—C5—C6 | 115.06 (16) | H16B—C16—H16C | 109.5 |
C3—C5—H5 | 107.7 | C15—C17—H17A | 109.5 |
C19—C5—H5 | 107.7 | C15—C17—H17B | 109.5 |
C6—C5—H5 | 107.7 | H17A—C17—H17B | 109.5 |
C7—C6—C11 | 108.71 (15) | C15—C17—H17C | 109.5 |
C7—C6—C5 | 110.13 (15) | H17A—C17—H17C | 109.5 |
C11—C6—C5 | 115.12 (15) | H17B—C17—H17C | 109.5 |
C7—C6—H6 | 107.5 | C10—C18—H18A | 109.5 |
C11—C6—H6 | 107.5 | C10—C18—H18B | 109.5 |
C5—C6—H6 | 107.5 | H18A—C18—H18B | 109.5 |
C8—C7—C6 | 116.43 (16) | C10—C18—H18C | 109.5 |
C8—C7—H7A | 108.2 | H18A—C18—H18C | 109.5 |
C6—C7—H7A | 108.2 | H18B—C18—H18C | 109.5 |
C8—C7—H7B | 108.2 | C5—C19—H19A | 109.5 |
C6—C7—H7B | 108.2 | C5—C19—H19B | 109.5 |
H7A—C7—H7B | 107.3 | H19A—C19—H19B | 109.5 |
O3—C8—C7 | 108.23 (15) | C5—C19—H19C | 109.5 |
O3—C8—C9 | 111.69 (15) | H19A—C19—H19C | 109.5 |
C7—C8—C9 | 112.61 (15) | H19B—C19—H19C | 109.5 |
O3—C8—H8 | 108.1 | C21—C20—C3 | 106.84 (18) |
C7—C8—H8 | 108.1 | C21—C20—H20 | 126.6 |
C9—C8—H8 | 108.1 | C3—C20—H20 | 126.6 |
O2—C9—C8 | 98.81 (14) | C20—C21—O1 | 110.47 (16) |
O2—C9—C10 | 107.73 (14) | C20—C21—H21 | 124.8 |
C8—C9—C10 | 112.52 (15) | O1—C21—H21 | 124.8 |
O2—C9—C15 | 106.84 (15) | O4—C22—O3 | 124.71 (18) |
C8—C9—C15 | 114.60 (15) | O4—C22—C23 | 125.53 (18) |
C10—C9—C15 | 114.68 (15) | O3—C22—C23 | 109.76 (16) |
C12—C10—C18 | 108.96 (15) | C24—C23—C22 | 121.45 (18) |
C12—C10—C11 | 108.84 (15) | C24—C23—H23 | 119.3 |
C18—C10—C11 | 108.63 (15) | C22—C23—H23 | 119.3 |
C12—C10—C9 | 108.74 (15) | C23—C24—C25 | 127.04 (19) |
C18—C10—C9 | 113.04 (15) | C23—C24—H24 | 116.5 |
C11—C10—C9 | 108.56 (14) | C25—C24—H24 | 116.5 |
C6—C11—C1 | 114.81 (15) | C26—C25—C30 | 118.55 (19) |
C6—C11—C10 | 110.32 (15) | C26—C25—C24 | 119.32 (19) |
C1—C11—C10 | 111.11 (15) | C30—C25—C24 | 122.08 (18) |
C6—C11—H11 | 106.7 | C27—C26—C25 | 120.8 (2) |
C1—C11—H11 | 106.7 | C27—C26—H26 | 119.6 |
C10—C11—H11 | 106.7 | C25—C26—H26 | 119.6 |
C13—C12—C10 | 113.86 (16) | C28—C27—C26 | 119.9 (2) |
C13—C12—H12A | 108.8 | C28—C27—H27 | 120.1 |
C10—C12—H12A | 108.8 | C26—C27—H27 | 120.1 |
C13—C12—H12B | 108.8 | C27—C28—C29 | 119.5 (2) |
C10—C12—H12B | 108.8 | C27—C28—H28 | 120.2 |
H12A—C12—H12B | 107.7 | C29—C28—H28 | 120.2 |
C14—C13—C12 | 111.37 (16) | C30—C29—C28 | 121.0 (2) |
C14—C13—H13A | 109.4 | C30—C29—H29 | 119.5 |
C12—C13—H13A | 109.4 | C28—C29—H29 | 119.5 |
C14—C13—H13B | 109.4 | C29—C30—C25 | 120.2 (2) |
C12—C13—H13B | 109.4 | C29—C30—H30 | 119.9 |
H13A—C13—H13B | 108.0 | C25—C30—H30 | 119.9 |
C21—O1—C2—C3 | −0.3 (2) | C12—C10—C11—C6 | 179.64 (15) |
C21—O1—C2—C1 | 177.67 (17) | C18—C10—C11—C6 | 61.13 (18) |
C11—C1—C2—C3 | −5.0 (3) | C9—C10—C11—C6 | −62.16 (18) |
C11—C1—C2—O1 | 177.44 (16) | C12—C10—C11—C1 | 51.1 (2) |
O1—C2—C3—C20 | 0.0 (2) | C18—C10—C11—C1 | −67.37 (19) |
C1—C2—C3—C20 | −177.72 (19) | C9—C10—C11—C1 | 169.34 (15) |
O1—C2—C3—C5 | −176.94 (16) | C18—C10—C12—C13 | −71.1 (2) |
C1—C2—C3—C5 | 5.3 (3) | C11—C10—C12—C13 | 170.62 (16) |
C2—C3—C5—C19 | 101.4 (2) | C9—C10—C12—C13 | 52.5 (2) |
C20—C3—C5—C19 | −74.6 (3) | C10—C12—C13—C14 | −54.4 (2) |
C2—C3—C5—C6 | −25.1 (2) | C12—C13—C14—C15 | 55.7 (2) |
C20—C3—C5—C6 | 158.87 (19) | C13—C14—C15—C17 | −173.02 (17) |
C3—C5—C6—C7 | 169.67 (16) | C13—C14—C15—C16 | 72.4 (2) |
C19—C5—C6—C7 | 46.4 (2) | C13—C14—C15—C9 | −54.3 (2) |
C3—C5—C6—C11 | 46.4 (2) | O2—C9—C15—C17 | 52.1 (2) |
C19—C5—C6—C11 | −77.0 (2) | C8—C9—C15—C17 | −56.2 (2) |
C11—C6—C7—C8 | −52.9 (2) | C10—C9—C15—C17 | 171.43 (16) |
C5—C6—C7—C8 | −179.92 (16) | O2—C9—C15—C16 | 174.00 (16) |
C22—O3—C8—C7 | −106.31 (17) | C8—C9—C15—C16 | 65.7 (2) |
C22—O3—C8—C9 | 129.17 (16) | C10—C9—C15—C16 | −66.7 (2) |
C6—C7—C8—O3 | −77.3 (2) | O2—C9—C15—C14 | −65.12 (18) |
C6—C7—C8—C9 | 46.7 (2) | C8—C9—C15—C14 | −173.46 (15) |
O3—C8—C9—O2 | −171.41 (13) | C10—C9—C15—C14 | 54.2 (2) |
C7—C8—C9—O2 | 66.56 (18) | C2—C3—C20—C21 | 0.3 (2) |
O3—C8—C9—C10 | 75.14 (18) | C5—C3—C20—C21 | 176.85 (19) |
C7—C8—C9—C10 | −46.9 (2) | C3—C20—C21—O1 | −0.5 (2) |
O3—C8—C9—C15 | −58.2 (2) | C2—O1—C21—C20 | 0.5 (2) |
C7—C8—C9—C15 | 179.73 (16) | C8—O3—C22—O4 | 0.7 (3) |
O2—C9—C10—C12 | 65.18 (19) | C8—O3—C22—C23 | −179.31 (15) |
C8—C9—C10—C12 | 173.04 (15) | O4—C22—C23—C24 | −5.4 (3) |
C15—C9—C10—C12 | −53.6 (2) | O3—C22—C23—C24 | 174.62 (18) |
O2—C9—C10—C18 | −173.68 (15) | C22—C23—C24—C25 | 179.95 (18) |
C8—C9—C10—C18 | −65.8 (2) | C23—C24—C25—C26 | −176.2 (2) |
C15—C9—C10—C18 | 67.5 (2) | C23—C24—C25—C30 | 1.2 (3) |
O2—C9—C10—C11 | −53.09 (19) | C30—C25—C26—C27 | −1.1 (3) |
C8—C9—C10—C11 | 54.77 (19) | C24—C25—C26—C27 | 176.37 (18) |
C15—C9—C10—C11 | −171.88 (16) | C25—C26—C27—C28 | −0.6 (3) |
C7—C6—C11—C1 | −173.43 (15) | C26—C27—C28—C29 | 1.6 (3) |
C5—C6—C11—C1 | −49.4 (2) | C27—C28—C29—C30 | −0.9 (3) |
C7—C6—C11—C10 | 60.11 (19) | C28—C29—C30—C25 | −0.8 (3) |
C5—C6—C11—C10 | −175.83 (15) | C26—C25—C30—C29 | 1.8 (3) |
C2—C1—C11—C6 | 26.3 (2) | C24—C25—C30—C29 | −175.65 (19) |
C2—C1—C11—C10 | 152.33 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.82 (3) | 2.28 (3) | 3.067 (2) | 160 (2) |
C18—H18A···O3 | 0.98 | 2.23 | 3.039 (2) | 139 |
Symmetry code: (i) x−1/2, −y−1/2, −z+1. |
Funding information
KOO is grateful to The University of Benin for a URPC 2016 grant, The World Academy of Sciences (TWAS) and the H. E. J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences (ICCBS), University of Karachi, Pakistan, for their financial and technical support through the ICCBS–TWAS Postdoctoral Fellowship program (reference No. 3240287190).
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