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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 8| August 2013| Page o1290
doi:10.1107/S1600536813019703

Isotenulin

Kyle S. Knight,a* Cole T. Smitha and Thomas G. Waddella

aDepartment of Chemistry, The University of Tennessee at Chattanooga, Chattanooga, TN 37403, USA
*Correspondence e-mail: kyle-knight@utc.edu

(Received 10 July 2013; accepted 16 July 2013; online 20 July 2013)

Isotenulin, C17H22O5, is a sesquiterpene lactone isolated from sneezeweed Helenium amarum. It crystallizes with two independent mol­ecules in the asymmetric unit. In each mol­ecule, two five-membered rings (cyclo­pentenone and lactone) are trans-fused to the central seven-membered ring. The five-membered rings each adopt envelope conformations. The seven-membered ring adopts a twist-chair conformation. In the crystal, the molecules are linked by C—H⋯O interactions, which generate a three-dimensional network.

Related literature

For the discovery and structural identification of tenulin, see: Clark (1939[Clark, E. P. (1939). J. Am. Chem. Soc. 61, 1836-1840.]); Herz et al. (1975[Herz, W. & Sharma, R. P. (1975). J. Org. Chem. 40, 2557-2559.]); Braun et al. (1956[Braun, B. H., Herz, W. & Rabindran, K. (1956). J. Am. Chem. Soc. 78, 4423-4429.]); Barton et al. (1956[Barton, D. H. R. & De Mayo, P. (1956). J. Chem. Soc. pp. 142-149.]). For biological activity that has been observed for tenulin and its analogs, see: Lee et al. (1977[Lee, K. H., Hall, I. H., Mar, E. C., Starnes, C. O., ElGebaly, S. A., Waddell, T. G., Hadgraft, R. I., Ruffner, C. G. & Weidner, I. (1977). Science, 196, 533-536.]); Li et al. (2008[Li, X.-J. & Zhang, H.-Y. (2008). Trends Mol. Med. 14, 1-2.]); Hodge et al. (1995[Hodge, J. S. & Waddell, T. G. (1995). J. Nat. Prod. 58, 149-151.], and references therein). For the crystal structure of tenulin, see: Knight et al. (2013[Knight, K. S., Smith, C. T., Waddell, T. G. & Noll, B. (2013). Acta Cryst. E69, o1237-o1238.]). For the crystal structure of bromo­isotenulin, see: Mazhar-Ul-Haque et al. (1974[Mazhar-Ul-Haque, Rogers, D. & Caughlan, C. N. (1974). J. Chem. Soc. Perkin Trans. 2, pp. 223-228.]).

[Scheme 1]

Experimental

Crystal data

  • C17H22O5

  • Mr = 306.34

  • Orthorhombic, P 21 21 21

  • a = 6.4565 (11) Å

  • b = 17.625 (3) Å

  • c = 27.997 (4) Å

  • V = 3186.0 (9) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 200 K

  • 0.55 × 0.3 × 0.2 mm
Data collection

  • Bruker APEXII CCD diffractometer

  • 34729 measured reflections

  • 5611 independent reflections

  • 4883 reflections with I > 2σ(I)

  • Rint = 0.047
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.100

  • S = 1.01

  • 5611 reflections

  • 405 parameters

  • H-atom parameters constrained

  • Δρmax = 0.13 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C4—H4⋯O4i 1.00 2.50 3.324 (4) 139
C21—H21⋯O5ii 1.00 2.44 3.421 (4) 167
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019703/cv5424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019703/cv5424Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019703/cv5424Isup3.cdx

checkCIF report


Comment top

Isotenulin, C17H22O5, is a sesquiterpene lactone isolated from sneezeweed Helenium amarum, a medicinal plant native to the southeastern USA. The crystal structure contains two independent tenulin molecules. These two conformations are distinguished by the way in which the five membered rings twist relative to each other, as measured by the magnitude of the dihedral angles at the cycloheptane-cyclopentenone and cycloheptane-lactone ring junctures. In the more twisted conformation, the dihedral angle of the substituents on the cycloheptane ring that form the cyclopentenone is 21.5 (1)°, while that of the lactone is 30.2 (1)°. Those values for the less twisted conformer are 18.1 (1)° and 28.2 (1)° respectively. The absolute configuration of all other stereocenters is that established for other sesquiterpene lactones (Mazhar-Ul-Haque et al., 1974).

Related literature top

For the discovery and structural identification of tenulin, see: Clark (1939); Herz et al. (1975); Braun et al. (1956); Barton et al. (1956). For biological activity that has been observed for tenulin and its analogs, see: Lee et al. (1977); Li et al. (2008); Hodge et al. (1995, and references therein). For the crystal structure of tenulin, see: Knight et al. (2013). For the crystal structure of bromoisotenulin, see: Mazhar-Ul-Haque et al. (1974).

Experimental top

Isotenulin was prepared as described previously (Hodge et al., 1995).

Refinement top

H atoms were positioned geometrically at bond distances of 0.98, 0.99, 1.00 and 0.95 Å for methyl, methylene, methine and vinyl, respectively, and constrained to ride on their parent atoms with Uiso(H)= 1.2–1.5 Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. Two independent molecules of isotenulin with the atomic numbering and displacement ellipsoids drawn at the 50% probability level.
(I) top
Crystal data top
C17H22O5Dx = 1.277 Mg m−3
Mr = 306.34Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 9402 reflections
a = 6.4565 (11) Åθ = 2.3–23.8°
b = 17.625 (3) ŵ = 0.09 mm−1
c = 27.997 (4) ÅT = 200 K
V = 3186.0 (9) Å3Block, colourless
Z = 80.55 × 0.3 × 0.2 mm
F(000) = 1312
Data collection top
Bruker APEXII CCD
diffractometer		Rint = 0.047
Graphite monochromatorθmax = 25.1°, θmin = 2.3°
ϕ and ω scansh = −7→7
34729 measured reflectionsk = −21→20
5611 independent reflectionsl = −31→31
4883 reflections with I > 2σ(I)
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0573P)2 + 0.5452P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
5611 reflectionsΔρmax = 0.13 e Å−3
405 parametersΔρmin = −0.17 e Å−3
Crystal data top
C17H22O5V = 3186.0 (9) Å3
Mr = 306.34Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 6.4565 (11) ŵ = 0.09 mm−1
b = 17.625 (3) ÅT = 200 K
c = 27.997 (4) Å0.55 × 0.3 × 0.2 mm
Data collection top
Bruker APEXII CCD
diffractometer		4883 reflections with I > 2σ(I)
34729 measured reflectionsRint = 0.047
5611 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.01Δρmax = 0.13 e Å−3
5611 reflectionsΔρmin = −0.17 e Å−3
405 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6652 (3)0.32092 (12)0.13792 (7)0.0282 (5)
O40.4353 (4)0.20905 (15)−0.02363 (8)0.0460 (6)
O20.4385 (4)0.33063 (13)−0.00295 (7)0.0384 (6)
O50.4353 (5)0.39087 (15)0.23006 (8)0.0521 (7)
O30.5852 (4)0.21748 (14)0.18164 (8)0.0437 (6)
O100.8514 (4)0.91154 (14)0.06402 (9)0.0426 (6)
O90.0773 (4)0.66834 (13)0.21828 (9)0.0470 (6)
O80.8155 (5)0.72399 (18)0.09136 (11)0.0705 (9)
O60.5119 (3)0.78613 (12)0.08363 (7)0.0322 (5)
O70.0566 (3)0.78753 (12)0.19284 (8)0.0342 (5)
C170.1123 (6)0.5589 (2)0.05783 (14)0.0489 (10)
H17A0.14400.57990.02630.073*
H17B0.10650.60000.08130.073*
H17C−0.02180.53290.05670.073*
C140.2811 (5)0.50237 (18)0.07211 (11)0.0333 (8)
H140.41500.53050.07500.040*
C130.2347 (5)0.46402 (17)0.12044 (10)0.0267 (7)
H130.12790.42410.11420.032*
C90.4208 (5)0.42363 (16)0.14536 (10)0.0256 (7)
C30.4490 (5)0.33964 (16)0.13131 (10)0.0241 (6)
H30.36550.30790.15380.029*
C20.7118 (5)0.26042 (19)0.16595 (12)0.0331 (7)
C80.9396 (6)0.2557 (2)0.17373 (14)0.0541 (10)
H8A0.98510.29900.19300.081*
H8B1.01080.25660.14280.081*
H8C0.97280.20840.19050.081*
C60.4421 (5)0.2565 (2)0.00761 (12)0.0355 (8)
C50.4467 (5)0.37680 (18)0.04092 (10)0.0316 (7)
H50.59100.39510.04680.038*
C150.3031 (5)0.44332 (19)0.03186 (11)0.0355 (8)
H15A0.16360.42290.02470.043*
H15B0.35200.47000.00280.043*
C120.1511 (5)0.51352 (18)0.16020 (12)0.0329 (7)
H120.05910.55470.15490.040*
C110.2185 (5)0.49380 (19)0.20298 (12)0.0363 (8)
H110.17810.51700.23220.044*
C100.3644 (5)0.43101 (18)0.19861 (11)0.0327 (7)
C40.3809 (4)0.32060 (16)0.08008 (10)0.0253 (6)
H40.22600.31900.08000.030*
C10.4563 (5)0.24438 (18)0.06090 (11)0.0324 (7)
H10.60580.23880.06950.039*
C70.3428 (6)0.17418 (18)0.07783 (12)0.0435 (9)
H7A0.19500.17910.07060.065*
H7B0.36130.16850.11240.065*
H7C0.39870.12950.06150.065*
C160.6230 (5)0.46954 (18)0.14028 (13)0.0364 (8)
H16A0.59500.52320.14680.055*
H16B0.67650.46410.10770.055*
H16C0.72580.45050.16310.055*
C270.7412 (5)0.94561 (18)0.09205 (11)0.0300 (7)
C260.5369 (4)0.91551 (16)0.11260 (10)0.0241 (6)
C200.5510 (5)0.83112 (16)0.12654 (9)0.0247 (6)
H200.69530.82050.13770.030*
C210.4003 (4)0.80785 (16)0.16622 (10)0.0245 (6)
H210.46360.82520.19690.029*
C180.3614 (5)0.72245 (17)0.17173 (11)0.0306 (7)
H180.34450.69990.13920.037*
C230.1542 (5)0.72034 (18)0.19676 (12)0.0344 (8)
C190.6589 (6)0.7361 (2)0.06999 (13)0.0448 (9)
C330.3809 (5)0.93110 (19)0.07173 (10)0.0317 (7)
H33A0.37520.98570.06530.048*
H33B0.24320.91310.08120.048*
H33C0.42550.90430.04280.048*
C280.7730 (5)1.02207 (18)0.11142 (12)0.0351 (8)
H280.87391.05730.10050.042*
C290.6391 (5)1.03451 (17)0.14657 (12)0.0329 (7)
H290.63201.08100.16360.039*
C300.4996 (4)0.96816 (16)0.15690 (10)0.0256 (7)
H300.55920.94140.18520.031*
C310.2724 (5)0.98620 (17)0.16899 (11)0.0290 (7)
H310.20091.00180.13890.035*
C320.1562 (5)0.91723 (17)0.18982 (11)0.0294 (7)
H32A0.20120.91090.22340.035*
H32B0.00670.92970.19040.035*
C220.1807 (5)0.84120 (17)0.16491 (11)0.0277 (7)
H220.12870.84410.13130.033*
C240.5304 (6)0.67908 (19)0.19779 (13)0.0439 (9)
H24A0.55800.70340.22860.066*
H24B0.65710.67920.17850.066*
H24C0.48530.62670.20310.066*
C340.2531 (6)1.05118 (18)0.20498 (13)0.0431 (9)
H34A0.32921.03820.23410.065*
H34B0.10671.05930.21270.065*
H34C0.31101.09760.19110.065*
C250.5960 (8)0.6984 (2)0.02392 (14)0.0628 (12)
H25A0.69920.66000.01530.094*
H25B0.58740.7365−0.00150.094*
H25C0.46060.67410.02800.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0238 (10)0.0339 (11)0.0271 (11)0.0024 (9)0.0006 (9)0.0045 (10)
O40.0406 (14)0.0598 (16)0.0378 (13)0.0078 (13)0.0003 (12)−0.0218 (12)
O20.0446 (14)0.0484 (15)0.0224 (11)0.0033 (12)0.0045 (10)−0.0046 (10)
O50.0764 (19)0.0547 (15)0.0253 (12)0.0087 (15)−0.0102 (13)−0.0023 (12)
O30.0402 (14)0.0408 (13)0.0500 (15)−0.0044 (12)−0.0046 (12)0.0171 (11)
O100.0275 (12)0.0566 (16)0.0438 (14)0.0042 (11)0.0089 (11)0.0024 (12)
O90.0493 (15)0.0327 (13)0.0590 (15)−0.0097 (12)0.0163 (13)0.0010 (12)
O80.063 (2)0.086 (2)0.0628 (19)0.0438 (17)−0.0031 (16)−0.0259 (17)
O60.0304 (12)0.0382 (12)0.0280 (11)0.0024 (9)0.0029 (9)−0.0120 (10)
O70.0278 (11)0.0319 (12)0.0429 (13)−0.0028 (10)0.0088 (10)−0.0016 (10)
C170.059 (2)0.044 (2)0.044 (2)0.0129 (19)−0.0084 (19)0.0053 (17)
C140.0392 (18)0.0320 (16)0.0285 (18)−0.0013 (14)−0.0037 (14)0.0026 (14)
C130.0236 (15)0.0277 (16)0.0288 (17)−0.0016 (13)−0.0004 (13)−0.0022 (13)
C90.0238 (15)0.0302 (15)0.0228 (15)−0.0024 (13)−0.0026 (13)−0.0015 (13)
C30.0186 (14)0.0303 (16)0.0234 (15)−0.0026 (12)0.0013 (12)0.0022 (12)
C20.0357 (18)0.0369 (18)0.0267 (16)0.0038 (15)0.0011 (15)0.0015 (15)
C80.035 (2)0.070 (3)0.057 (2)0.016 (2)−0.0001 (18)0.019 (2)
C60.0241 (16)0.048 (2)0.0341 (18)0.0061 (16)0.0003 (14)−0.0122 (17)
C50.0324 (16)0.0404 (18)0.0220 (15)−0.0027 (15)0.0017 (14)−0.0022 (14)
C150.042 (2)0.0411 (19)0.0234 (17)−0.0022 (16)−0.0004 (14)0.0082 (14)
C120.0257 (15)0.0316 (16)0.042 (2)−0.0012 (14)0.0022 (15)−0.0049 (15)
C110.0374 (19)0.0398 (19)0.0318 (19)−0.0045 (16)0.0051 (15)−0.0116 (15)
C100.0355 (18)0.0369 (18)0.0256 (17)−0.0076 (15)−0.0063 (15)−0.0037 (15)
C40.0198 (14)0.0303 (16)0.0259 (15)−0.0009 (12)0.0001 (12)−0.0010 (13)
C10.0292 (16)0.0366 (17)0.0314 (16)0.0091 (15)−0.0046 (14)−0.0071 (14)
C70.058 (2)0.0315 (18)0.041 (2)0.0013 (17)−0.0110 (18)−0.0045 (16)
C160.0296 (17)0.0351 (17)0.044 (2)−0.0045 (15)−0.0028 (16)−0.0010 (16)
C270.0206 (15)0.0419 (18)0.0275 (17)0.0050 (14)−0.0042 (14)0.0056 (15)
C260.0170 (14)0.0342 (17)0.0210 (15)0.0031 (13)−0.0050 (12)−0.0019 (13)
C200.0189 (14)0.0304 (16)0.0247 (15)0.0025 (13)−0.0031 (12)−0.0071 (13)
C210.0256 (15)0.0258 (14)0.0221 (15)−0.0002 (12)−0.0017 (13)−0.0049 (12)
C180.0335 (17)0.0277 (15)0.0306 (17)−0.0016 (14)0.0029 (14)−0.0059 (14)
C230.0380 (18)0.0299 (17)0.0353 (18)−0.0071 (16)0.0027 (16)−0.0099 (15)
C190.050 (2)0.043 (2)0.041 (2)0.0078 (18)0.0134 (19)−0.0092 (17)
C330.0275 (16)0.0452 (19)0.0224 (17)0.0022 (14)−0.0025 (13)−0.0002 (14)
C280.0246 (16)0.0370 (18)0.0436 (19)−0.0042 (14)−0.0036 (15)0.0138 (16)
C290.0300 (16)0.0282 (16)0.0405 (19)0.0006 (14)−0.0107 (15)0.0021 (14)
C300.0282 (16)0.0245 (15)0.0241 (16)0.0030 (12)−0.0053 (12)0.0001 (12)
C310.0299 (16)0.0312 (16)0.0259 (16)0.0050 (13)0.0015 (14)0.0007 (14)
C320.0253 (15)0.0330 (16)0.0299 (17)0.0064 (13)0.0041 (14)−0.0017 (13)
C220.0256 (16)0.0320 (16)0.0256 (15)−0.0030 (13)0.0027 (13)0.0008 (13)
C240.041 (2)0.0335 (18)0.057 (2)0.0031 (17)0.0045 (18)0.0076 (18)
C340.057 (2)0.0284 (17)0.044 (2)0.0022 (17)0.0137 (18)−0.0048 (16)
C250.076 (3)0.062 (3)0.051 (2)0.003 (2)0.015 (2)−0.030 (2)
Geometric parameters (Å, º) top
O1—C31.446 (3)C1—C71.514 (5)
O1—C21.358 (4)C7—H7A0.9800
O4—C61.211 (4)C7—H7B0.9800
O2—C61.340 (4)C7—H7C0.9800
O2—C51.474 (4)C16—H16A0.9800
O5—C101.219 (4)C16—H16B0.9800
O3—C21.198 (4)C16—H16C0.9800
O10—C271.218 (4)C27—C261.533 (4)
O9—C231.204 (4)C27—C281.467 (5)
O8—C191.194 (5)C26—C201.540 (4)
O6—C201.462 (3)C26—C331.549 (4)
O6—C191.350 (4)C26—C301.568 (4)
O7—C231.346 (4)C20—H201.0000
O7—C221.466 (4)C20—C211.533 (4)
C17—H17A0.9800C21—H211.0000
C17—H17B0.9800C21—C181.534 (4)
C17—H17C0.9800C21—C221.535 (4)
C17—C141.530 (5)C18—H181.0000
C14—H141.0000C18—C231.511 (5)
C14—C131.542 (4)C18—C241.519 (5)
C14—C151.540 (5)C19—C251.507 (5)
C13—H131.0000C33—H33A0.9800
C13—C91.561 (4)C33—H33B0.9800
C13—C121.514 (4)C33—H33C0.9800
C9—C31.542 (4)C28—H280.9500
C9—C101.540 (4)C28—C291.328 (5)
C9—C161.542 (4)C29—H290.9500
C3—H31.0000C29—C301.504 (4)
C3—C41.537 (4)C30—H301.0000
C2—C81.489 (5)C30—C311.539 (4)
C8—H8A0.9800C31—H311.0000
C8—H8B0.9800C31—C321.543 (4)
C8—H8C0.9800C31—C341.530 (4)
C6—C11.510 (5)C32—H32A0.9900
C5—H51.0000C32—H32B0.9900
C5—C151.516 (5)C32—C221.519 (4)
C5—C41.537 (4)C22—H221.0000
C15—H15A0.9900C24—H24A0.9800
C15—H15B0.9900C24—H24B0.9800
C12—H120.9500C24—H24C0.9800
C12—C111.321 (5)C34—H34A0.9800
C11—H110.9500C34—H34B0.9800
C11—C101.459 (5)C34—H34C0.9800
C4—H41.0000C25—H25A0.9800
C4—C11.526 (4)C25—H25B0.9800
C1—H11.0000C25—H25C0.9800
C2—O1—C3117.8 (2)H16A—C16—H16C109.5
C6—O2—C5110.7 (2)H16B—C16—H16C109.5
C19—O6—C20117.7 (3)O10—C27—C26125.0 (3)
C23—O7—C22110.8 (2)O10—C27—C28127.6 (3)
H17A—C17—H17B109.5C28—C27—C26107.4 (3)
H17A—C17—H17C109.5C27—C26—C20112.2 (2)
H17B—C17—H17C109.5C27—C26—C33102.8 (2)
C14—C17—H17A109.5C27—C26—C30103.0 (2)
C14—C17—H17B109.5C20—C26—C33113.4 (2)
C14—C17—H17C109.5C20—C26—C30112.3 (2)
C17—C14—H14108.3C33—C26—C30112.3 (2)
C17—C14—C13112.1 (3)O6—C20—C26107.8 (2)
C17—C14—C15108.3 (3)O6—C20—H20108.4
C13—C14—H14108.3O6—C20—C21109.9 (2)
C15—C14—H14108.3C26—C20—H20108.4
C15—C14—C13111.3 (3)C21—C20—C26113.9 (2)
C14—C13—H13106.8C21—C20—H20108.4
C14—C13—C9116.3 (3)C20—C21—H21106.3
C9—C13—H13106.8C20—C21—C18116.1 (2)
C12—C13—C14117.5 (3)C20—C21—C22117.8 (2)
C12—C13—H13106.8C18—C21—H21106.3
C12—C13—C9102.0 (2)C18—C21—C22103.1 (2)
C3—C9—C13114.5 (2)C22—C21—H21106.3
C10—C9—C13102.3 (2)C21—C18—H18108.4
C10—C9—C3110.8 (2)C23—C18—C21102.5 (2)
C10—C9—C16104.2 (2)C23—C18—H18108.4
C16—C9—C13111.8 (2)C23—C18—C24113.6 (3)
C16—C9—C3112.3 (2)C24—C18—C21115.1 (3)
O1—C3—C9107.5 (2)C24—C18—H18108.4
O1—C3—H3108.2O9—C23—O7121.2 (3)
O1—C3—C4110.2 (2)O9—C23—C18128.0 (3)
C9—C3—H3108.2O7—C23—C18110.8 (3)
C4—C3—C9114.4 (2)O8—C19—O6124.8 (3)
C4—C3—H3108.2O8—C19—C25125.3 (3)
O1—C2—C8110.3 (3)O6—C19—C25109.9 (4)
O3—C2—O1123.8 (3)C26—C33—H33A109.5
O3—C2—C8125.8 (3)C26—C33—H33B109.5
C2—C8—H8A109.5C26—C33—H33C109.5
C2—C8—H8B109.5H33A—C33—H33B109.5
C2—C8—H8C109.5H33A—C33—H33C109.5
H8A—C8—H8B109.5H33B—C33—H33C109.5
H8A—C8—H8C109.5C27—C28—H28125.2
H8B—C8—H8C109.5C29—C28—C27109.5 (3)
O4—C6—O2120.9 (3)C29—C28—H28125.2
O4—C6—C1128.2 (3)C28—C29—H29123.1
O2—C6—C1110.9 (3)C28—C29—C30113.8 (3)
O2—C5—H5110.4C30—C29—H29123.1
O2—C5—C15105.4 (2)C26—C30—H30106.8
O2—C5—C4103.2 (2)C29—C30—C26102.5 (2)
C15—C5—H5110.4C29—C30—H30106.8
C15—C5—C4116.7 (3)C29—C30—C31116.9 (2)
C4—C5—H5110.4C31—C30—C26116.3 (2)
C14—C15—H15A108.0C31—C30—H30106.8
C14—C15—H15B108.0C30—C31—H31108.1
C5—C15—C14117.2 (3)C30—C31—C32112.6 (2)
C5—C15—H15A108.0C32—C31—H31108.1
C5—C15—H15B108.0C34—C31—C30112.1 (3)
H15A—C15—H15B107.2C34—C31—H31108.1
C13—C12—H12123.3C34—C31—C32107.5 (3)
C11—C12—C13113.4 (3)C31—C32—H32A107.8
C11—C12—H12123.3C31—C32—H32B107.8
C12—C11—H11125.2H32A—C32—H32B107.1
C12—C11—C10109.7 (3)C22—C32—C31118.1 (2)
C10—C11—H11125.2C22—C32—H32A107.8
O5—C10—C9124.2 (3)C22—C32—H32B107.8
O5—C10—C11128.5 (3)O7—C22—C21104.2 (2)
C11—C10—C9107.3 (3)O7—C22—C32105.5 (2)
C3—C4—C5116.5 (2)O7—C22—H22110.6
C3—C4—H4107.1C21—C22—H22110.6
C5—C4—H4107.1C32—C22—C21115.0 (3)
C1—C4—C3115.4 (2)C32—C22—H22110.6
C1—C4—C5103.2 (2)C18—C24—H24A109.5
C1—C4—H4107.1C18—C24—H24B109.5
C6—C1—C4101.8 (2)C18—C24—H24C109.5
C6—C1—H1108.1H24A—C24—H24B109.5
C6—C1—C7113.3 (3)H24A—C24—H24C109.5
C4—C1—H1108.1H24B—C24—H24C109.5
C7—C1—C4117.0 (3)C31—C34—H34A109.5
C7—C1—H1108.1C31—C34—H34B109.5
C1—C7—H7A109.5C31—C34—H34C109.5
C1—C7—H7B109.5H34A—C34—H34B109.5
C1—C7—H7C109.5H34A—C34—H34C109.5
H7A—C7—H7B109.5H34B—C34—H34C109.5
H7A—C7—H7C109.5C19—C25—H25A109.5
H7B—C7—H7C109.5C19—C25—H25B109.5
C9—C16—H16A109.5C19—C25—H25C109.5
C9—C16—H16B109.5H25A—C25—H25B109.5
C9—C16—H16C109.5H25A—C25—H25C109.5
H16A—C16—H16B109.5H25B—C25—H25C109.5
O1—C3—C4—C5−77.5 (3)C10—C9—C3—C4146.2 (3)
O1—C3—C4—C143.8 (3)C4—C5—C15—C1466.5 (4)
O4—C6—C1—C4−160.3 (3)C16—C9—C3—O125.0 (3)
O4—C6—C1—C7−33.7 (5)C16—C9—C3—C4−97.7 (3)
O2—C6—C1—C420.1 (3)C16—C9—C10—O5−84.0 (4)
O2—C6—C1—C7146.6 (3)C16—C9—C10—C1195.2 (3)
O2—C5—C15—C14−179.7 (3)C27—C26—C20—O6−84.3 (3)
O2—C5—C4—C3157.7 (2)C27—C26—C20—C21153.5 (2)
O2—C5—C4—C130.2 (3)C27—C26—C30—C2918.1 (3)
O10—C27—C26—C2041.9 (4)C27—C26—C30—C31146.9 (3)
O10—C27—C26—C33−80.3 (3)C27—C28—C29—C301.1 (4)
O10—C27—C26—C30162.9 (3)C26—C27—C28—C2911.6 (3)
O10—C27—C28—C29−169.9 (3)C26—C20—C21—C18163.0 (2)
O6—C20—C21—C1842.0 (3)C26—C20—C21—C2240.0 (3)
O6—C20—C21—C22−81.0 (3)C26—C30—C31—C3271.5 (3)
C17—C14—C13—C9−163.2 (3)C26—C30—C31—C34−167.1 (3)
C17—C14—C13—C12−42.0 (4)C20—O6—C19—O82.8 (5)
C17—C14—C15—C5−173.7 (3)C20—O6—C19—C25−177.0 (3)
C14—C13—C9—C3−89.3 (3)C20—C26—C30—C29139.1 (2)
C14—C13—C9—C10150.7 (3)C20—C26—C30—C31−92.2 (3)
C14—C13—C9—C1639.8 (4)C20—C21—C18—C23−157.5 (2)
C14—C13—C12—C11−144.6 (3)C20—C21—C18—C2478.6 (3)
C13—C14—C15—C5−50.0 (4)C20—C21—C22—O7157.5 (2)
C13—C9—C3—O1153.9 (2)C20—C21—C22—C32−87.5 (3)
C13—C9—C3—C431.1 (3)C21—C18—C23—O9−162.1 (3)
C13—C9—C10—O5159.5 (3)C21—C18—C23—O717.2 (3)
C13—C9—C10—C11−21.3 (3)C18—C21—C22—O728.2 (3)
C13—C12—C11—C102.7 (4)C18—C21—C22—C32143.2 (3)
C9—C13—C12—C11−16.2 (3)C23—O7—C22—C21−18.7 (3)
C9—C3—C4—C543.8 (3)C23—O7—C22—C32−140.3 (3)
C9—C3—C4—C1165.0 (3)C19—O6—C20—C26122.9 (3)
C3—O1—C2—O37.6 (4)C19—O6—C20—C21−112.5 (3)
C3—O1—C2—C8−172.7 (3)C33—C26—C20—O631.6 (3)
C3—C9—C10—O537.0 (4)C33—C26—C20—C21−90.6 (3)
C3—C9—C10—C11−143.8 (3)C33—C26—C30—C29−91.7 (3)
C3—C4—C1—C6−158.2 (3)C33—C26—C30—C3137.0 (4)
C3—C4—C1—C777.8 (4)C28—C27—C26—C20−139.5 (2)
C2—O1—C3—C9125.7 (3)C28—C27—C26—C3398.3 (3)
C2—O1—C3—C4−109.0 (3)C28—C27—C26—C30−18.5 (3)
C6—O2—C5—C15−141.7 (3)C28—C29—C30—C26−12.8 (3)
C6—O2—C5—C4−18.8 (3)C28—C29—C30—C31−141.1 (3)
C5—O2—C6—O4179.6 (3)C29—C30—C31—C32−167.1 (3)
C5—O2—C6—C1−0.8 (4)C29—C30—C31—C34−45.7 (4)
C5—C4—C1—C6−30.0 (3)C30—C26—C20—O6160.3 (2)
C5—C4—C1—C7−154.1 (3)C30—C26—C20—C2138.0 (3)
C15—C14—C13—C975.2 (3)C30—C31—C32—C22−46.3 (4)
C15—C14—C13—C12−163.5 (3)C31—C32—C22—O7179.2 (3)
C15—C5—C4—C3−87.3 (3)C31—C32—C22—C2165.0 (4)
C15—C5—C4—C1145.2 (3)C22—O7—C23—O9−179.7 (3)
C12—C13—C9—C3141.5 (3)C22—O7—C23—C180.9 (3)
C12—C13—C9—C1021.5 (3)C22—C21—C18—C23−27.1 (3)
C12—C13—C9—C16−89.4 (3)C22—C21—C18—C24−151.0 (3)
C12—C11—C10—O5−168.5 (4)C24—C18—C23—O9−37.3 (5)
C12—C11—C10—C912.4 (4)C24—C18—C23—O7142.1 (3)
C10—C9—C3—O1−91.1 (3)C34—C31—C32—C22−170.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O4i1.002.503.324 (4)139
C21—H21···O5ii1.002.443.421 (4)167
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O4i1.002.503.324 (4)139.1
C21—H21···O5ii1.002.443.421 (4)167.3
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+1, y+1/2, −z+1/2.
 

Acknowledgements

Acknowledgements are made to the National Science Foundation MRI Program (CHE-0951711) and the Grote Chemistry Fund at the University of Tennessee at Chattanooga for their generous support of our work.

References

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ISSN: 2056-9890
Volume 69| Part 8| August 2013| Page o1290
doi:10.1107/S1600536813019703
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