organic compounds
Methyl 3,5-bis(cyclohexylmethoxy)benzoate
aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA
*Correspondence e-mail: pcorfield@fordham.edu
In the title compound, C22H32O4, the atoms of the methyl ester group and the alkoxy O atoms are all coplanar with the central aromatic ring, with an r.m.s. deviation of 0.008 Å. Bonds to the methylene and cyclohexyl groups are also very close to this plane, so that the molecule is essentially flat, apart from the cyclohexyl groups. The mean planes through the cyclohexyl groups are tilted by 30.08 (9) and 36.14 (7)° with respect to the central aromatic ring. In the crystal, pairs of molecules linked by C—H⋯O hydrogen bonds form planar units which are stacked along the a axis, with an average interplanar distance of 3.549 (2) Å. Stacking appears to be stabilized by further weak C—H⋯O hydrogen bonds.
CCDC reference: 989172
Related literature
The title compound was synthesized as a monomer for novel dendrimers, as part of a continuing study of how dendrimers effectively complex with organic pollutants in aqueous environments. For a project review, see: Monaco et al. (2013); Corfield & Balija (2013). For a review of the role of C—H⋯O hydrogen bonds in organic reactions, see: Johnston & Cheong (2013). For an example of an organic involving the cyclohexylmethoxybenzene fragment, see: Yang et al. (2008).
Experimental
Crystal data
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Data collection: CAD-4 (Enraf–Nonius, 1994); cell CAD-4; data reduction: followed procedures in Corfield et al. (1973) and data were averaged with a local version of SORTAV (Blessing, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 989172
10.1107/S1600536814004607/pk2519sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814004607/pk2519Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814004607/pk2519Isup3.cml
The reaction was performed under an argon gas atmosphere with oven dried glassware. Reagents were obtained from Aldrich and used without further purification.
solvent ratios are reported in v/v.1H NMR spectra were recorded at 300 MHz and 13C NMR spectra were recorded at 75 MHz on a Bruker AV-300 High Performance Digital NMR Spectrometer. Chemical shifts are reported in parts per million (ppm) and coupling constants in Hertz (Hz). 1H NMR spectra obtained in CDCl3 were referenced to 7.26 ppm and 13C NMR spectra obtained in CDCl3 were referenced to 77.2 ppm. Mass spectra were obtained from University of Illinois
Center (Micromass Q-TOF Ultra, ESI).To a heterogeneous mixture of 8.50 g (61.5 mmol) of K2CO3 in DMF (37.5 mL) were added 5.00 g (29.7 mmol) of methyl 3,5-dihydroxy benzoate. After 2 hours, 8.80 mL (63.1 mmol) of bromomethylcyclohexane were added over 10 min and the reaction heated at 80oC for 3 h. Upon cooling the reaction to room temperature, ethyl acetate (100 mL) was added and the organic layer was washed with water (5X, 70 mL) and brine (1X, 70 mL). The organic layer was dried with anhydrous sodium sulfate and the solvent was removed in vacuo. The resulting mixture of methyl 3-cyclohexylmethoxy-5-hydroxybenzoate and methyl 3,5-bis(cyclohexylmethoxy)benzoate was separated by
(silica gel, petroleum ether:diethyl ether, 1:1). The title product was obtained as a yellow oil and allowed to sit undisturbed over several months, when colorless crystals separated, mp 70.6-72.8°C.1H NMR peaks δ: 7.15 (d, J = 2.3, 2H), 6.63 (t, J = 2.3, 1H), 3.91 (s, 3H), 3.77 (d, J = 6.2, 4H), 1.88-1.03 (m, 22H). 13C NMR peaks δ: 167.00, 160.6, 132.0, 107.9, 107.0, 73.8, 52.3, 37.6, 29.8, 26.5, 25.8. HRMS-ESI: m/z [M + H]+ C22H33O4 361.2390; found 361.2379.
Both forms of the 0 1 0 and of the 0 0 1 reflections were partially obscured by the beam stop, and were omitted from the refinements. H atoms were constrained to idealized positions with C—H distances of 0.93Å for the aromatic H atoms, 0.96Å for the methyl H atoms, 0.97Å for the secondary H atoms and 0.98Å for the tertiary H atoms on C10 and C17. The orientation of the methyl group was determined by calculation of electron density in the toroid that should contain the H atoms of the idealized methyl group. The Ueq values for all H atoms were fixed at 1.2 times the Uiso of their bonded C atoms.
Dendrimers are macromolecules prepared in a stepwise fashion from monomer units and a core molecule. This work is part of a larger study examining how the the modification of functional groups in the monomer impacts the physical and chemical properties of the resulting dendrimer. The title compound is an intermediate for a novel cyclohexane based dendrimer (Monaco et al., 2013; Corfield and Balija, 2013).
In the title compound, C22H32O4, the four atoms of the methyl ester group and the two oxygen atoms of the 3,5 alkoxy substituents are all coplanar with the central aromatic ring, with a dihedral angle of the ester group to the ring of only 0.7 (1)°. Bonds to the cyclohexyl groups are also close to this plane, with torsional angles C2—C3—O1—C9 and C3—O1—C9—C10 of 172.88 (15)° and 179.66 (14)° respectively, and C6—C5—O2—C16 and C5—O2—C16—C17 angles of 3.4 (3)° and 175.59 (14)° respectively. The C10—C15 and C17—C22 cyclohexyl groups are oriented respectively away from and towards the methyl ester group on C1 (Fig. 1), and their mean planes are tilted 30.08 (9)° and 36.14 (7)° to the central aromatic ring. A similar extended conformation for the cyclohexylmethoxy substituent in a related compound is found in Yang et al. (2008).
Steric repulsion between methylene hydrogen atoms of the alkoxy groups and ring protons leads to opening of the exterior ring angles to 124.6 (1)° and 24.8 (1)°, and of the bond angles at the ether oxygen atoms to 118.7 (1)° and 117.9 (1)°.
Pairs of molecules are connected by weak C—H··· O hydrogen bonds across the center of symmetry at (1 - x, 1 - y, 1 - z). (Figs. 2 and 3) The central planes of the symmetry-related molecules are almost coplanar, with a perpendicular distance between them of 0.105 (3)Å. The molecular pairs are stacked along the a axis, with average interplanar spacing of 3.549 (2) Å. (Fig. 4) There are no obvious π—π interactions to explain the short stacking distance. We propose that part of the interplanar interaction arises from the presence of long C—H···O hydrogen bonds between O3 and methylene and cyclohexyl hydrogen atoms H16A and H18A. (See Table 1) Such non-classical hydrogen bonds are frequently invoked in recent publications in this journal, and their impact on reaction stereochemistry is reviewed in Johnston and Cheong (2013).
Data collection: CAD-4 (Enraf–Nonius, 1994); cell
CAD-4 (Enraf–Nonius, 1994); data reduction: followed procedures in Corfield et al. (1973) and data were averaged with a local version of SORTAV (Blessing, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C22H32O4 | Z = 2 |
Mr = 360.48 | F(000) = 392 |
Triclinic, P1 | Dx = 1.162 Mg m−3 |
Hall symbol: -P 1 | Melting point: 344.8 K |
a = 6.649 (1) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 12.668 (1) Å | Cell parameters from 25 reflections |
c = 12.873 (1) Å | θ = 3.2–9.7° |
α = 87.64 (1)° | µ = 0.08 mm−1 |
β = 79.46 (1)° | T = 298 K |
γ = 75.06 (1)° | Block, colourless |
V = 1029.9 (2) Å3 | 0.75 × 0.75 × 0.53 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.008 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.3° |
Graphite monochromator | h = −1→8 |
θ/2θ scans | k = −15→15 |
5155 measured reflections | l = −15→15 |
4051 independent reflections | 3 standard reflections every 120 min |
3013 reflections with I > 2σ(I) | intensity decay: 1.3(5) |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.270P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
4051 reflections | Δρmax = 0.17 e Å−3 |
237 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (2) |
C22H32O4 | γ = 75.06 (1)° |
Mr = 360.48 | V = 1029.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.649 (1) Å | Mo Kα radiation |
b = 12.668 (1) Å | µ = 0.08 mm−1 |
c = 12.873 (1) Å | T = 298 K |
α = 87.64 (1)° | 0.75 × 0.75 × 0.53 mm |
β = 79.46 (1)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.008 |
5155 measured reflections | 3 standard reflections every 120 min |
4051 independent reflections | intensity decay: 1.3(5) |
3013 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
4051 reflections | Δρmin = −0.14 e Å−3 |
237 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 | −0.2343 (2) | 0.20265 (10) | 0.34241 (8) | 0.0613 (3) | |
O2 | −0.0616 (2) | 0.25640 (11) | 0.67501 (8) | 0.0628 (4) | |
O3 | 0.2878 (2) | 0.42136 (12) | 0.25302 (9) | 0.0756 (4) | |
O4 | 0.37753 (19) | 0.44700 (10) | 0.40594 (8) | 0.0602 (3) | |
C1 | 0.1250 (2) | 0.34685 (12) | 0.40804 (11) | 0.0450 (4) | |
C2 | 0.0091 (3) | 0.30219 (13) | 0.35244 (11) | 0.0486 (4) | |
H2 | 0.0217 | 0.3118 | 0.2797 | 0.058* | |
C3 | −0.1264 (3) | 0.24282 (13) | 0.40479 (11) | 0.0490 (4) | |
C4 | −0.1455 (3) | 0.22817 (14) | 0.51302 (12) | 0.0512 (4) | |
H4 | −0.2355 | 0.1878 | 0.5482 | 0.061* | |
C5 | −0.0280 (3) | 0.27471 (13) | 0.56870 (11) | 0.0495 (4) | |
C6 | 0.1076 (3) | 0.33363 (13) | 0.51749 (11) | 0.0485 (4) | |
H6 | 0.1862 | 0.3641 | 0.5549 | 0.058* | |
C7 | 0.2697 (3) | 0.40810 (13) | 0.34645 (12) | 0.0483 (4) | |
C8 | 0.5185 (3) | 0.50921 (17) | 0.35207 (14) | 0.0655 (5) | |
H8A | 0.6079 | 0.4683 | 0.2922 | 0.079* | |
H8B | 0.6042 | 0.5236 | 0.3995 | 0.079* | |
H8C | 0.4372 | 0.5771 | 0.3286 | 0.079* | |
C9 | −0.3584 (3) | 0.13030 (15) | 0.38765 (12) | 0.0554 (4) | |
H9A | −0.4655 | 0.1661 | 0.4459 | 0.067* | |
H9B | −0.2692 | 0.0658 | 0.4145 | 0.067* | |
C10 | −0.4621 (3) | 0.09842 (14) | 0.30275 (12) | 0.0516 (4) | |
H10 | −0.5436 | 0.1657 | 0.2746 | 0.062* | |
C11 | −0.3030 (3) | 0.03691 (16) | 0.21158 (14) | 0.0621 (5) | |
H11A | −0.2114 | 0.0823 | 0.1795 | 0.075* | |
H11B | −0.2157 | −0.0286 | 0.2379 | 0.075* | |
C12 | −0.4151 (4) | 0.00567 (19) | 0.12867 (16) | 0.0777 (6) | |
H12A | −0.3110 | −0.0377 | 0.0735 | 0.093* | |
H12B | −0.4894 | 0.0714 | 0.0967 | 0.093* | |
C13 | −0.5711 (4) | −0.05892 (19) | 0.17717 (19) | 0.0862 (7) | |
H13A | −0.6463 | −0.0733 | 0.1237 | 0.103* | |
H13B | −0.4946 | −0.1286 | 0.2016 | 0.103* | |
C14 | −0.7281 (4) | 0.00134 (19) | 0.26845 (18) | 0.0795 (6) | |
H14A | −0.8190 | −0.0444 | 0.3005 | 0.095* | |
H14B | −0.8163 | 0.0670 | 0.2428 | 0.095* | |
C15 | −0.6158 (3) | 0.03203 (17) | 0.35076 (15) | 0.0665 (5) | |
H15A | −0.7197 | 0.0742 | 0.4067 | 0.080* | |
H15B | −0.5395 | −0.0339 | 0.3816 | 0.080* | |
C16 | 0.0433 (3) | 0.30659 (15) | 0.73897 (11) | 0.0525 (4) | |
H16A | 0.0098 | 0.3849 | 0.7276 | 0.063* | |
H16B | 0.1953 | 0.2778 | 0.7200 | 0.063* | |
C17 | −0.0299 (3) | 0.28262 (14) | 0.85363 (11) | 0.0500 (4) | |
H17 | 0.0038 | 0.2032 | 0.8626 | 0.060* | |
C18 | −0.2652 (3) | 0.32768 (16) | 0.88989 (12) | 0.0571 (4) | |
H18A | −0.3025 | 0.4059 | 0.8784 | 0.069* | |
H18B | −0.3411 | 0.2949 | 0.8482 | 0.069* | |
C19 | −0.3324 (3) | 0.3047 (2) | 1.00661 (13) | 0.0713 (6) | |
H19A | −0.4822 | 0.3385 | 1.0281 | 0.086* | |
H19B | −0.3101 | 0.2265 | 1.0167 | 0.086* | |
C20 | −0.2097 (3) | 0.3479 (2) | 1.07503 (13) | 0.0755 (6) | |
H20A | −0.2480 | 0.4271 | 1.0729 | 0.091* | |
H20B | −0.2473 | 0.3259 | 1.1476 | 0.091* | |
C21 | 0.0244 (3) | 0.3063 (2) | 1.03912 (14) | 0.0855 (7) | |
H21A | 0.0658 | 0.2281 | 1.0511 | 0.103* | |
H21B | 0.0976 | 0.3409 | 1.0807 | 0.103* | |
C22 | 0.0908 (3) | 0.3291 (2) | 0.92233 (13) | 0.0706 (6) | |
H22A | 0.0649 | 0.4073 | 0.9117 | 0.085* | |
H22B | 0.2413 | 0.2969 | 0.9010 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0823 (8) | 0.0788 (8) | 0.0403 (6) | −0.0437 (7) | −0.0227 (6) | 0.0013 (5) |
O2 | 0.0878 (9) | 0.0868 (9) | 0.0294 (5) | −0.0490 (7) | −0.0117 (5) | −0.0017 (5) |
O3 | 0.1073 (11) | 0.0992 (10) | 0.0400 (7) | −0.0588 (9) | −0.0200 (6) | 0.0126 (6) |
O4 | 0.0700 (8) | 0.0812 (8) | 0.0408 (6) | −0.0389 (7) | −0.0108 (5) | −0.0017 (5) |
C1 | 0.0534 (9) | 0.0468 (8) | 0.0358 (7) | −0.0132 (7) | −0.0093 (6) | −0.0030 (6) |
C2 | 0.0623 (10) | 0.0546 (9) | 0.0326 (7) | −0.0175 (8) | −0.0140 (7) | −0.0004 (6) |
C3 | 0.0596 (10) | 0.0563 (9) | 0.0364 (7) | −0.0190 (8) | −0.0150 (7) | −0.0059 (7) |
C4 | 0.0612 (10) | 0.0616 (10) | 0.0379 (8) | −0.0272 (8) | −0.0092 (7) | −0.0034 (7) |
C5 | 0.0618 (10) | 0.0586 (10) | 0.0311 (7) | −0.0193 (8) | −0.0094 (6) | −0.0058 (6) |
C6 | 0.0580 (9) | 0.0581 (10) | 0.0349 (7) | −0.0208 (8) | −0.0122 (7) | −0.0056 (6) |
C7 | 0.0581 (9) | 0.0508 (9) | 0.0376 (8) | −0.0144 (7) | −0.0108 (7) | −0.0023 (6) |
C8 | 0.0700 (12) | 0.0821 (13) | 0.0543 (10) | −0.0387 (10) | −0.0084 (9) | −0.0001 (9) |
C9 | 0.0628 (10) | 0.0688 (11) | 0.0424 (8) | −0.0274 (9) | −0.0130 (7) | −0.0026 (8) |
C10 | 0.0554 (9) | 0.0567 (10) | 0.0491 (9) | −0.0192 (8) | −0.0186 (7) | −0.0024 (7) |
C11 | 0.0644 (11) | 0.0728 (12) | 0.0551 (10) | −0.0219 (9) | −0.0170 (8) | −0.0115 (8) |
C12 | 0.0951 (15) | 0.0896 (15) | 0.0598 (11) | −0.0326 (12) | −0.0261 (11) | −0.0183 (10) |
C13 | 0.1146 (18) | 0.0749 (14) | 0.0933 (16) | −0.0410 (13) | −0.0549 (14) | −0.0056 (12) |
C14 | 0.0806 (14) | 0.0876 (15) | 0.0923 (16) | −0.0464 (12) | −0.0389 (12) | 0.0143 (12) |
C15 | 0.0657 (12) | 0.0796 (13) | 0.0647 (11) | −0.0324 (10) | −0.0199 (9) | 0.0060 (10) |
C16 | 0.0600 (10) | 0.0700 (11) | 0.0344 (8) | −0.0261 (8) | −0.0110 (7) | −0.0060 (7) |
C17 | 0.0632 (10) | 0.0591 (10) | 0.0320 (7) | −0.0201 (8) | −0.0122 (7) | −0.0030 (6) |
C18 | 0.0603 (10) | 0.0788 (12) | 0.0414 (8) | −0.0310 (9) | −0.0132 (7) | 0.0013 (8) |
C19 | 0.0726 (12) | 0.1068 (16) | 0.0428 (9) | −0.0418 (12) | −0.0042 (8) | 0.0003 (9) |
C20 | 0.0836 (14) | 0.1131 (17) | 0.0355 (9) | −0.0389 (13) | −0.0022 (8) | −0.0136 (9) |
C21 | 0.0782 (14) | 0.148 (2) | 0.0381 (9) | −0.0345 (14) | −0.0178 (9) | −0.0129 (11) |
C22 | 0.0581 (11) | 0.1212 (17) | 0.0398 (9) | −0.0323 (11) | −0.0101 (8) | −0.0153 (10) |
O1—C3 | 1.3608 (17) | C12—H12A | 0.9700 |
O1—C9 | 1.4245 (19) | C12—H12B | 0.9700 |
O2—C5 | 1.3658 (18) | C13—C14 | 1.506 (3) |
O2—C16 | 1.4322 (17) | C13—H13A | 0.9700 |
O3—C7 | 1.1959 (18) | C13—H13B | 0.9700 |
O4—C7 | 1.3256 (18) | C14—C15 | 1.518 (2) |
O4—C8 | 1.4415 (19) | C14—H14A | 0.9700 |
C1—C2 | 1.373 (2) | C14—H14B | 0.9700 |
C1—C6 | 1.399 (2) | C15—H15A | 0.9700 |
C1—C7 | 1.487 (2) | C15—H15B | 0.9700 |
C2—C3 | 1.385 (2) | C16—C17 | 1.511 (2) |
C2—H2 | 0.9300 | C16—H16A | 0.9700 |
C3—C4 | 1.385 (2) | C16—H16B | 0.9700 |
C4—C5 | 1.396 (2) | C17—C22 | 1.523 (2) |
C4—H4 | 0.9300 | C17—C18 | 1.512 (2) |
C5—C6 | 1.376 (2) | C17—H17 | 0.9800 |
C6—H6 | 0.9300 | C18—C19 | 1.526 (2) |
C8—H8A | 0.9600 | C18—H18A | 0.9700 |
C8—H8B | 0.9600 | C18—H18B | 0.9700 |
C8—H8C | 0.9600 | C19—C20 | 1.508 (2) |
C9—C10 | 1.513 (2) | C19—H19A | 0.9700 |
C9—H9A | 0.9700 | C19—H19B | 0.9700 |
C9—H9B | 0.9700 | C20—C21 | 1.499 (3) |
C10—C15 | 1.518 (2) | C20—H20A | 0.9700 |
C10—C11 | 1.516 (2) | C20—H20B | 0.9700 |
C10—H10 | 0.9800 | C21—C22 | 1.525 (2) |
C11—C12 | 1.526 (2) | C21—H21A | 0.9700 |
C11—H11A | 0.9700 | C21—H21B | 0.9700 |
C11—H11B | 0.9700 | C22—H22A | 0.9700 |
C12—C13 | 1.514 (3) | C22—H22B | 0.9700 |
C3—O1—C9 | 118.71 (12) | C14—C13—H13B | 109.3 |
C5—O2—C16 | 117.86 (12) | C12—C13—H13B | 109.3 |
C7—O4—C8 | 116.24 (12) | H13A—C13—H13B | 107.9 |
C2—C1—C6 | 120.88 (14) | C13—C14—C15 | 110.87 (17) |
C2—C1—C7 | 116.97 (13) | C13—C14—H14A | 109.5 |
C6—C1—C7 | 122.15 (13) | C15—C14—H14A | 109.5 |
C1—C2—C3 | 119.89 (14) | C13—C14—H14B | 109.5 |
C1—C2—H2 | 120.1 | C15—C14—H14B | 109.5 |
C3—C2—H2 | 120.1 | H14A—C14—H14B | 108.1 |
O1—C3—C4 | 124.58 (14) | C10—C15—C14 | 111.39 (16) |
O1—C3—C2 | 115.13 (13) | C10—C15—H15A | 109.3 |
C4—C3—C2 | 120.28 (14) | C14—C15—H15A | 109.3 |
C3—C4—C5 | 119.23 (15) | C10—C15—H15B | 109.3 |
C3—C4—H4 | 120.4 | C14—C15—H15B | 109.3 |
C5—C4—H4 | 120.4 | H15A—C15—H15B | 108.0 |
O2—C5—C6 | 124.79 (13) | O2—C16—C17 | 108.62 (13) |
O2—C5—C4 | 114.21 (14) | O2—C16—H16A | 110.0 |
C6—C5—C4 | 121.00 (13) | C17—C16—H16A | 110.0 |
C5—C6—C1 | 118.70 (14) | O2—C16—H16B | 110.0 |
C5—C6—H6 | 120.6 | C17—C16—H16B | 110.0 |
C1—C6—H6 | 120.6 | H16A—C16—H16B | 108.3 |
O3—C7—O4 | 123.11 (15) | C16—C17—C22 | 109.33 (14) |
O3—C7—C1 | 123.90 (14) | C16—C17—C18 | 113.02 (14) |
O4—C7—C1 | 112.99 (12) | C22—C17—C18 | 109.76 (13) |
O4—C8—H8A | 109.5 | C16—C17—H17 | 108.2 |
O4—C8—H8B | 109.5 | C22—C17—H17 | 108.2 |
H8A—C8—H8B | 109.5 | C18—C17—H17 | 108.2 |
O4—C8—H8C | 109.5 | C19—C18—C17 | 111.55 (15) |
H8A—C8—H8C | 109.5 | C19—C18—H18A | 109.3 |
H8B—C8—H8C | 109.5 | C17—C18—H18A | 109.3 |
O1—C9—C10 | 108.22 (13) | C19—C18—H18B | 109.3 |
O1—C9—H9A | 110.1 | C17—C18—H18B | 109.3 |
C10—C9—H9A | 110.1 | H18A—C18—H18B | 108.0 |
O1—C9—H9B | 110.1 | C20—C19—C18 | 111.71 (15) |
C10—C9—H9B | 110.1 | C20—C19—H19A | 109.3 |
H9A—C9—H9B | 108.4 | C18—C19—H19A | 109.3 |
C9—C10—C15 | 109.83 (14) | C20—C19—H19B | 109.3 |
C9—C10—C11 | 112.77 (14) | C18—C19—H19B | 109.3 |
C15—C10—C11 | 110.74 (15) | H19A—C19—H19B | 107.9 |
C9—C10—H10 | 107.8 | C21—C20—C19 | 111.69 (16) |
C15—C10—H10 | 107.8 | C21—C20—H20A | 109.3 |
C11—C10—H10 | 107.8 | C19—C20—H20A | 109.3 |
C12—C11—C10 | 110.79 (15) | C21—C20—H20B | 109.3 |
C12—C11—H11A | 109.5 | C19—C20—H20B | 109.3 |
C10—C11—H11A | 109.5 | H20A—C20—H20B | 107.9 |
C12—C11—H11B | 109.5 | C20—C21—C22 | 111.75 (17) |
C10—C11—H11B | 109.5 | C20—C21—H21A | 109.3 |
H11A—C11—H11B | 108.1 | C22—C21—H21A | 109.3 |
C11—C12—C13 | 111.22 (17) | C20—C21—H21B | 109.3 |
C11—C12—H12A | 109.4 | C22—C21—H21B | 109.3 |
C13—C12—H12A | 109.4 | H21A—C21—H21B | 107.9 |
C11—C12—H12B | 109.4 | C17—C22—C21 | 111.58 (16) |
C13—C12—H12B | 109.4 | C17—C22—H22A | 109.3 |
H12A—C12—H12B | 108.0 | C21—C22—H22A | 109.3 |
C14—C13—C12 | 111.78 (17) | C17—C22—H22B | 109.3 |
C14—C13—H13A | 109.3 | C21—C22—H22B | 109.3 |
C12—C13—H13A | 109.3 | H22A—C22—H22B | 108.0 |
C2—C3—O1—C9 | 172.88 (15) | C4—C5—O2—C16 | −176.46 (15) |
C4—C3—O1—C9 | −7.4 (3) | C6—C5—O2—C16 | 3.3 (3) |
C3—O1—C9—C10 | 179.66 (14) | C5—O2—C16—C17 | 175.59 (14) |
O1—C9—C10—C11 | 62.55 (19) | O2—C16—C17—C18 | −61.10 (19) |
O1—C9—C10—C15 | −173.41 (15) | O2—C16—C17—C22 | 176.33 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O4i | 0.96 | 2.58 | 3.409 (2) | 145 |
C16—H16A···O3ii | 0.97 | 2.71 | 3.573 (2) | 148 |
C18—H18A···O3ii | 0.97 | 2.72 | 3.590 (2) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O4i | 0.96 | 2.58 | 3.409 (2) | 145.2 |
C16—H16A···O3ii | 0.97 | 2.71 | 3.573 (2) | 147.9 |
C18—H18A···O3ii | 0.97 | 2.72 | 3.590 (2) | 149.4 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
Acknowledgements
We are grateful for the Dean's Office at Fordham University for its generous financial support. We thank Matthew P. Tracey for his assistance with this work. The Q-Tof Ultima
(University of Illinois at Urbana-Champaign) was purchased in part with a grant from the NSF, Division of Biological Infrastructure (DBI-0100085).References
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