research communications
Crystal structures of 6-cyclopropyl-1,3-diphenylfulvene and 6-(2,3-dimethoxynaphthyl)-1,3-diphenylfulvene
aDepartment of Chemistry & Chemistry Research Center, United States Air Force, Academy, Colorado Springs, CO 80840, USA
*Correspondence e-mail: Gary.Balaich@usafa.edu
The title compounds, 6-cyclopropyl-1,3-diphenylfulvene, C21H18, [systematic name: 5-(cyclopropylmethylidene)-1,3-diphenylcyclopenta-1,3-diene], 1, and 6-(2,3-dimethoxynaphthyl)-1,3-diphenylfulvene, C30H24O2, {systematic name: 5-[(3,4-dimethoxynaphthalen-2-yl)methylidene]-1,3-diphenylcyclopenta-1,3-diene}, 2, were prepared from 1,3-diphenylcyclopentadiene, pyrrolidine, and the corresponding in an ethanolic solution. Each structure crystallizes with one molecule per and exhibits the alternating short and long bond lengths typical of A network of C—H⋯C ring interactions as well as C—H⋯O interactions is observed, resulting in the compact packing found in each structure.
Keywords: crystal structure; fulvene; C—H⋯C ring interactions.
1. Chemical context
Pentafulvenes are a unique class of cross-conjugated organic molecules commonly synthesized using aldehyde and cyclopentadiene starting materials under a variety of conditions (Thiele, 1900; Stone & Little, 1984; Sieverding et al., 2019). Substituted and highly colored pentafulvenes are of particular interest because of their unique optical and thermal properties and for their potential use in electronic applications (Peloquin et al., 2012; Godman et al., 2016; Shurdha et al., 2014). In synthetic organometallic chemistry, the fulvene unit is known to coordinate to metals, forming organometallic complexes of varying hapticity (Peloquin et al., 2018; Ma et al., 2011, 2012; Beckhaus, 2018). More recently, 1,3,6-trisubstituted have been used as starting materials in the synthesis of bridged cyclopentadiene ligands and ansa-Ln complexes (Adas & Balaich, 2018). As a continuation of our work in this area, we report herein the crystal structures of 6-cyclopropyl-1,3-diphenylfulvene, 1, and 6-(2,3-dimethoxynaphthyl)-1,3-diphenylfulvene, 2.
2. Structural commentary
Compounds 1 (Fig. 1) and 2 (Fig. 2) crystallize in the orthorhombic space groups Pbca and P212121, respectively. Both crystallize with one molecule per (Z′ = 1), exhibit the expected alternating short–long bond lengths within the fulvene core and display very similar bond lengths and angles (Table 1). Similar tilt angles of the phenyl substituents from the plane of the fulvene ring are also observed for 1 [1-Ph, 44.88 (4)°; 3-Ph 13.34 (4)°] and 2 [1-Ph, 30.82 (7)°; 3-Ph 17.19 (7)°]. Surprisingly, the rotation of the 6-substituent from the cyclopentadienyl core is greater for fulvene 1 [87.20 (6)°], than for the larger 2,3-dimethoxynaphthalene substituent in fulvene 2, [55.63 (5)°].
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3. Supramolecular features
Fulvene 1 packs side by side along the a-axis direction with molecules oriented in such a way that the 6-cyclopropyl groups are sandwiched between the 1-Ph and 3-Ph rings of adjacent fulvene molecules. The closest contacts caused by this stacking sequence in the a-axis direction are between the 1-Ph ring atom H9 and the exocyclic C6 atom of an adjacent fulvene (C—H⋯C = 2.90 Å). Other C—H⋯C contacts (C12⋯H19 = 2.83, C2⋯H10 = 2.85, C14⋯H20B = 2.85, C11⋯H19 = 2.86 Å) lead to the formation of a network that results in sets of zigzag chains running perpendicular to the a-axis direction and that extend in the direction parallel to the bc plane (Fig. 3).
Fulvene 2 packs so that the 1-Ph groups are oriented towards the space between the 2,3-dimethoxynaphthyl groups and the 3-Ph rings of adjacent fulvene molecules along the b-axis direction. A view down the a axis (Fig. 4) reveals layers of interlaced 2,3-dimethoxynaphthyl groups (H, head) oriented H–H and separated from layers of interlaced 1,3-diphenylfulvene groups (T, tail) oriented T–T, with the layers running perpendicular to the c-axis direction and producing a layer sequence of H–H–T–T along the c-axis direction. In the H–H layers, short intermolecular contacts of the C—H⋯O type (O1⋯H22 = 2.50 and O2⋯H24 = 2.53 Å; Table 2) occur between adjacent 2,3-dimethoxynaphthyl groups running along the b-axis direction (Fig. 4). The methoxy groups apparently prevent the naphthyl rings from forming any π–π stacking interactions, with the angle between the mean planes of the 2,3-dimethoxynaphthyl groups oriented at 124.37 (5)° at least partially enforced by the C—H⋯O interactions.
4. Database survey
A survey of the December 2019 release of the Cambridge Structural Database, with updates through November 2019, was made using the program Conquest (Groom et al., 2016). A search for 1,3-diphenyl-6-substituted yielded 88 results. The bond lengths and angles in 1 and 2 are consistent with those in the previously reported literature.
5. Synthesis and crystallization
Each compound was prepared according to the established literature procedure (Peloquin et al., 2012; Godman et al., 2016).
6-(Cyclopropyl)-1,3-diphenylfulvene, 1. Orange crystals suitable for single crystal X-ray diffraction were obtained from petroleum ether by slow evaporation.
6-(2,3-Dimethoxynapthyl)-1,3-diphenylfulvene, 2. Red crystals suitable for single crystal X-ray diffraction were obtained from slow diffusion of petroleum ether into a DCM solution.
6. Refinement
Crystal data, data collection and structure . H atoms were placed in calculated positions (0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl).
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989020006441/yk2129sup1.cif
contains datablocks 1, 2. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989020006441/yk21291sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989020006441/yk21292sup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020006441/yk21291sup4.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2056989020006441/yk21291sup5.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020006441/yk21292sup6.cml
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2019); cell
CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C21H18 | Dx = 1.194 Mg m−3 |
Mr = 270.35 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 50470 reflections |
a = 12.9844 (2) Å | θ = 2.1–27.4° |
b = 11.9583 (1) Å | µ = 0.07 mm−1 |
c = 19.3729 (2) Å | T = 100 K |
V = 3008.06 (6) Å3 | Block, orange |
Z = 8 | 0.38 × 0.25 × 0.15 mm |
F(000) = 1152 |
XtaLAB Synergy, Single source at offset/far, HyPix3000 diffractometer | 3353 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 2967 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.030 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.4°, θmin = 2.1° |
ω scans | h = −16→16 |
Absorption correction: empirical (using intensity measurements) (CrysAlisPro; Rigaku OD, 2019) | k = −15→15 |
Tmin = 0.404, Tmax = 1.000 | l = −24→24 |
74031 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.7758P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3353 reflections | Δρmax = 0.20 e Å−3 |
190 parameters | Δρmin = −0.19 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.44298 (7) | 0.64490 (8) | 0.32819 (5) | 0.0198 (2) | |
C2 | 0.50655 (7) | 0.60105 (8) | 0.37681 (5) | 0.0203 (2) | |
H2 | 0.5051 | 0.6191 | 0.4246 | 0.024* | |
C3 | 0.57790 (7) | 0.52136 (8) | 0.34441 (5) | 0.0204 (2) | |
C4 | 0.55715 (7) | 0.51958 (8) | 0.27550 (5) | 0.0227 (2) | |
H4 | 0.5918 | 0.4750 | 0.2422 | 0.027* | |
C5 | 0.47342 (7) | 0.59679 (8) | 0.26098 (5) | 0.0216 (2) | |
C6 | 0.43760 (7) | 0.62688 (8) | 0.19814 (5) | 0.0224 (2) | |
H6 | 0.3823 | 0.6788 | 0.1965 | 0.027* | |
C7 | 0.35860 (7) | 0.72504 (8) | 0.33954 (5) | 0.0207 (2) | |
C8 | 0.26145 (8) | 0.70904 (9) | 0.30946 (5) | 0.0249 (2) | |
H8 | 0.2502 | 0.6466 | 0.2801 | 0.030* | |
C9 | 0.18165 (8) | 0.78343 (9) | 0.32221 (5) | 0.0293 (2) | |
H9 | 0.1163 | 0.7718 | 0.3013 | 0.035* | |
C10 | 0.19672 (8) | 0.87480 (9) | 0.36532 (6) | 0.0316 (2) | |
H10 | 0.1422 | 0.9260 | 0.3737 | 0.038* | |
C11 | 0.29212 (8) | 0.89076 (9) | 0.39608 (6) | 0.0298 (2) | |
H11 | 0.3026 | 0.9526 | 0.4260 | 0.036* | |
C12 | 0.37234 (8) | 0.81683 (8) | 0.38334 (5) | 0.0242 (2) | |
H12 | 0.4373 | 0.8287 | 0.4046 | 0.029* | |
C13 | 0.65376 (7) | 0.45139 (8) | 0.38061 (5) | 0.0214 (2) | |
C14 | 0.65376 (7) | 0.44071 (8) | 0.45261 (5) | 0.0240 (2) | |
H14 | 0.6078 | 0.4848 | 0.4794 | 0.029* | |
C15 | 0.72009 (8) | 0.36649 (8) | 0.48540 (5) | 0.0278 (2) | |
H15 | 0.7187 | 0.3597 | 0.5343 | 0.033* | |
C16 | 0.78805 (9) | 0.30253 (9) | 0.44717 (6) | 0.0311 (2) | |
H16 | 0.8319 | 0.2503 | 0.4696 | 0.037* | |
C17 | 0.79200 (9) | 0.31494 (9) | 0.37585 (6) | 0.0318 (2) | |
H17 | 0.8400 | 0.2727 | 0.3495 | 0.038* | |
C18 | 0.72593 (8) | 0.38887 (8) | 0.34322 (5) | 0.0269 (2) | |
H18 | 0.7296 | 0.3974 | 0.2945 | 0.032* | |
C19 | 0.47766 (8) | 0.58544 (8) | 0.13271 (5) | 0.0245 (2) | |
H19 | 0.5338 | 0.5284 | 0.1360 | 0.029* | |
C20 | 0.48463 (8) | 0.66600 (9) | 0.07225 (5) | 0.0268 (2) | |
H20A | 0.4598 | 0.7434 | 0.0795 | 0.032* | |
H20B | 0.5447 | 0.6592 | 0.0411 | 0.032* | |
C21 | 0.40700 (9) | 0.57559 (9) | 0.07072 (5) | 0.0298 (2) | |
H21A | 0.4188 | 0.5125 | 0.0386 | 0.036* | |
H21B | 0.3339 | 0.5968 | 0.0769 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0211 (4) | 0.0180 (4) | 0.0203 (4) | −0.0038 (3) | 0.0031 (3) | −0.0006 (3) |
C2 | 0.0216 (4) | 0.0199 (4) | 0.0194 (4) | −0.0045 (4) | 0.0023 (3) | −0.0010 (3) |
C3 | 0.0212 (4) | 0.0181 (4) | 0.0218 (5) | −0.0036 (4) | 0.0017 (4) | 0.0002 (3) |
C4 | 0.0256 (5) | 0.0218 (5) | 0.0208 (5) | 0.0028 (4) | 0.0020 (4) | −0.0006 (4) |
C5 | 0.0236 (5) | 0.0202 (4) | 0.0209 (5) | −0.0002 (4) | 0.0021 (4) | −0.0007 (4) |
C6 | 0.0236 (5) | 0.0213 (5) | 0.0223 (5) | 0.0019 (4) | 0.0016 (4) | 0.0001 (4) |
C7 | 0.0232 (5) | 0.0203 (4) | 0.0187 (4) | −0.0013 (4) | 0.0045 (4) | 0.0026 (3) |
C8 | 0.0246 (5) | 0.0271 (5) | 0.0230 (5) | −0.0025 (4) | 0.0035 (4) | 0.0011 (4) |
C9 | 0.0225 (5) | 0.0363 (6) | 0.0291 (5) | 0.0013 (4) | 0.0040 (4) | 0.0068 (4) |
C10 | 0.0300 (5) | 0.0297 (5) | 0.0350 (6) | 0.0086 (4) | 0.0107 (4) | 0.0063 (4) |
C11 | 0.0359 (6) | 0.0217 (5) | 0.0318 (5) | 0.0025 (4) | 0.0073 (4) | −0.0014 (4) |
C12 | 0.0267 (5) | 0.0211 (5) | 0.0248 (5) | −0.0016 (4) | 0.0026 (4) | 0.0006 (4) |
C13 | 0.0221 (4) | 0.0184 (4) | 0.0237 (5) | −0.0039 (4) | −0.0019 (4) | −0.0003 (4) |
C14 | 0.0234 (5) | 0.0243 (5) | 0.0244 (5) | −0.0057 (4) | −0.0002 (4) | 0.0007 (4) |
C15 | 0.0312 (5) | 0.0272 (5) | 0.0252 (5) | −0.0087 (4) | −0.0065 (4) | 0.0046 (4) |
C16 | 0.0321 (5) | 0.0248 (5) | 0.0366 (6) | −0.0004 (4) | −0.0138 (5) | 0.0019 (4) |
C17 | 0.0314 (6) | 0.0292 (5) | 0.0348 (6) | 0.0074 (4) | −0.0080 (4) | −0.0071 (4) |
C18 | 0.0290 (5) | 0.0277 (5) | 0.0240 (5) | 0.0028 (4) | −0.0036 (4) | −0.0037 (4) |
C19 | 0.0285 (5) | 0.0250 (5) | 0.0199 (5) | 0.0059 (4) | −0.0001 (4) | −0.0002 (4) |
C20 | 0.0300 (5) | 0.0298 (5) | 0.0207 (5) | 0.0005 (4) | 0.0025 (4) | 0.0014 (4) |
C21 | 0.0327 (5) | 0.0344 (6) | 0.0223 (5) | −0.0031 (4) | −0.0024 (4) | −0.0032 (4) |
C1—C2 | 1.3577 (13) | C11—C12 | 1.3882 (14) |
C1—C5 | 1.4774 (13) | C12—H12 | 0.9500 |
C1—C7 | 1.4721 (13) | C13—C14 | 1.4008 (14) |
C2—H2 | 0.9500 | C13—C18 | 1.4006 (14) |
C2—C3 | 1.4699 (13) | C14—H14 | 0.9500 |
C3—C4 | 1.3621 (13) | C14—C15 | 1.3903 (14) |
C3—C13 | 1.4704 (13) | C15—H15 | 0.9500 |
C4—H4 | 0.9500 | C15—C16 | 1.3829 (16) |
C4—C5 | 1.4538 (13) | C16—H16 | 0.9500 |
C5—C6 | 1.3520 (13) | C16—C17 | 1.3905 (16) |
C6—H6 | 0.9500 | C17—H17 | 0.9500 |
C6—C19 | 1.4570 (13) | C17—C18 | 1.3847 (14) |
C7—C8 | 1.4027 (14) | C18—H18 | 0.9500 |
C7—C12 | 1.3988 (13) | C19—H19 | 1.0000 |
C8—H8 | 0.9500 | C19—C20 | 1.5193 (14) |
C8—C9 | 1.3879 (14) | C19—C21 | 1.5159 (14) |
C9—H9 | 0.9500 | C20—H20A | 0.9900 |
C9—C10 | 1.3891 (16) | C20—H20B | 0.9900 |
C10—H10 | 0.9500 | C20—C21 | 1.4784 (15) |
C10—C11 | 1.3878 (16) | C21—H21A | 0.9900 |
C11—H11 | 0.9500 | C21—H21B | 0.9900 |
C2—C1—C5 | 107.36 (8) | C14—C13—C3 | 121.79 (9) |
C2—C1—C7 | 126.89 (9) | C18—C13—C3 | 120.35 (9) |
C7—C1—C5 | 125.75 (8) | C18—C13—C14 | 117.80 (9) |
C1—C2—H2 | 125.1 | C13—C14—H14 | 119.6 |
C1—C2—C3 | 109.71 (8) | C15—C14—C13 | 120.88 (9) |
C3—C2—H2 | 125.1 | C15—C14—H14 | 119.6 |
C2—C3—C13 | 125.97 (8) | C14—C15—H15 | 119.9 |
C4—C3—C2 | 107.70 (8) | C16—C15—C14 | 120.24 (10) |
C4—C3—C13 | 126.23 (9) | C16—C15—H15 | 119.9 |
C3—C4—H4 | 125.4 | C15—C16—H16 | 120.1 |
C3—C4—C5 | 109.12 (8) | C15—C16—C17 | 119.78 (10) |
C5—C4—H4 | 125.4 | C17—C16—H16 | 120.1 |
C4—C5—C1 | 106.08 (8) | C16—C17—H17 | 120.0 |
C6—C5—C1 | 126.72 (9) | C18—C17—C16 | 119.93 (10) |
C6—C5—C4 | 126.91 (9) | C18—C17—H17 | 120.0 |
C5—C6—H6 | 117.6 | C13—C18—H18 | 119.4 |
C5—C6—C19 | 124.75 (9) | C17—C18—C13 | 121.28 (10) |
C19—C6—H6 | 117.6 | C17—C18—H18 | 119.4 |
C8—C7—C1 | 121.23 (9) | C6—C19—H19 | 115.9 |
C12—C7—C1 | 120.44 (9) | C6—C19—C20 | 118.44 (9) |
C12—C7—C8 | 118.28 (9) | C6—C19—C21 | 119.97 (9) |
C7—C8—H8 | 119.7 | C20—C19—H19 | 115.9 |
C9—C8—C7 | 120.66 (10) | C21—C19—H19 | 115.9 |
C9—C8—H8 | 119.7 | C21—C19—C20 | 58.30 (7) |
C8—C9—H9 | 119.8 | C19—C20—H20A | 117.7 |
C8—C9—C10 | 120.40 (10) | C19—C20—H20B | 117.7 |
C10—C9—H9 | 119.8 | H20A—C20—H20B | 114.8 |
C9—C10—H10 | 120.3 | C21—C20—C19 | 60.74 (7) |
C11—C10—C9 | 119.48 (10) | C21—C20—H20A | 117.7 |
C11—C10—H10 | 120.3 | C21—C20—H20B | 117.7 |
C10—C11—H11 | 119.8 | C19—C21—H21A | 117.7 |
C10—C11—C12 | 120.38 (10) | C19—C21—H21B | 117.7 |
C12—C11—H11 | 119.8 | C20—C21—C19 | 60.96 (7) |
C7—C12—H12 | 119.6 | C20—C21—H21A | 117.7 |
C11—C12—C7 | 120.79 (10) | C20—C21—H21B | 117.7 |
C11—C12—H12 | 119.6 | H21A—C21—H21B | 114.8 |
C30H24O2 | Dx = 1.267 Mg m−3 |
Mr = 416.49 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 35583 reflections |
a = 7.3431 (1) Å | θ = 1.9–27.3° |
b = 11.5468 (1) Å | µ = 0.08 mm−1 |
c = 25.7555 (3) Å | T = 100 K |
V = 2183.79 (4) Å3 | Block, red |
Z = 4 | 0.27 × 0.15 × 0.13 mm |
F(000) = 880 |
XtaLAB Synergy, Single source at offset/far, HyPix3000 diffractometer | 4798 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 4437 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.036 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.4°, θmin = 1.9° |
ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (CrysAlisPro; Rigaku OD, 2019) | k = −14→14 |
Tmin = 0.735, Tmax = 1.000 | l = −32→32 |
54562 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0415P)2 + 0.3848P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.082 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.16 e Å−3 |
4798 reflections | Δρmin = −0.18 e Å−3 |
291 parameters | Absolute structure: Flack x determined using 1774 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.3 (4) |
Primary atom site location: dual |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.44518 (18) | 0.62766 (11) | 0.68257 (5) | 0.0247 (3) | |
O2 | 0.61050 (17) | 0.49358 (11) | 0.75201 (5) | 0.0259 (3) | |
C1 | −0.0406 (2) | 0.65397 (15) | 0.55785 (7) | 0.0198 (4) | |
C2 | −0.0799 (2) | 0.59770 (15) | 0.51299 (7) | 0.0211 (4) | |
H2 | −0.1346 | 0.6322 | 0.4834 | 0.025* | |
C3 | −0.0254 (2) | 0.47506 (15) | 0.51698 (7) | 0.0197 (4) | |
C4 | 0.0428 (3) | 0.45757 (16) | 0.56522 (6) | 0.0207 (4) | |
H4 | 0.0855 | 0.3857 | 0.5784 | 0.025* | |
C5 | 0.0400 (2) | 0.56652 (15) | 0.59360 (6) | 0.0196 (4) | |
C6 | 0.1117 (2) | 0.58571 (15) | 0.64113 (7) | 0.0204 (4) | |
H6 | 0.1098 | 0.6635 | 0.6531 | 0.024* | |
C7 | −0.0696 (2) | 0.77839 (15) | 0.56788 (7) | 0.0201 (4) | |
C8 | −0.1120 (3) | 0.82200 (15) | 0.61722 (7) | 0.0232 (4) | |
H8 | −0.1192 | 0.7705 | 0.6459 | 0.028* | |
C9 | −0.1436 (3) | 0.93976 (16) | 0.62481 (8) | 0.0276 (4) | |
H9 | −0.1710 | 0.9678 | 0.6586 | 0.033* | |
C10 | −0.1352 (3) | 1.01607 (17) | 0.58346 (8) | 0.0302 (4) | |
H10 | −0.1570 | 1.0963 | 0.5887 | 0.036* | |
C11 | −0.0945 (3) | 0.97418 (17) | 0.53435 (8) | 0.0302 (4) | |
H11 | −0.0895 | 1.0260 | 0.5058 | 0.036* | |
C12 | −0.0612 (3) | 0.85764 (16) | 0.52664 (7) | 0.0252 (4) | |
H12 | −0.0321 | 0.8307 | 0.4928 | 0.030* | |
C13 | −0.0383 (2) | 0.38948 (15) | 0.47494 (6) | 0.0198 (4) | |
C14 | −0.1483 (3) | 0.40870 (16) | 0.43146 (7) | 0.0240 (4) | |
H14 | −0.2167 | 0.4783 | 0.4289 | 0.029* | |
C15 | −0.1585 (3) | 0.32715 (17) | 0.39190 (7) | 0.0274 (4) | |
H15 | −0.2351 | 0.3408 | 0.3628 | 0.033* | |
C16 | −0.0574 (3) | 0.22612 (16) | 0.39474 (7) | 0.0252 (4) | |
H16 | −0.0638 | 0.1707 | 0.3675 | 0.030* | |
C17 | 0.0532 (3) | 0.20609 (16) | 0.43754 (7) | 0.0243 (4) | |
H17 | 0.1233 | 0.1371 | 0.4395 | 0.029* | |
C18 | 0.0617 (3) | 0.28622 (16) | 0.47734 (7) | 0.0229 (4) | |
H18 | 0.1363 | 0.2711 | 0.5067 | 0.028* | |
C19 | 0.1926 (2) | 0.49925 (15) | 0.67648 (7) | 0.0194 (4) | |
C20 | 0.3601 (2) | 0.52592 (15) | 0.69714 (7) | 0.0206 (4) | |
C21 | 0.4485 (3) | 0.45362 (15) | 0.73404 (6) | 0.0211 (4) | |
C22 | 0.3672 (3) | 0.35129 (15) | 0.74809 (7) | 0.0216 (4) | |
H22 | 0.4269 | 0.3012 | 0.7719 | 0.026* | |
C23 | 0.1953 (3) | 0.31938 (15) | 0.72749 (6) | 0.0198 (4) | |
C24 | 0.1143 (3) | 0.21256 (16) | 0.74162 (7) | 0.0233 (4) | |
H24 | 0.1763 | 0.1620 | 0.7647 | 0.028* | |
C25 | −0.0526 (3) | 0.18134 (16) | 0.72228 (7) | 0.0254 (4) | |
H25 | −0.1043 | 0.1087 | 0.7314 | 0.030* | |
C26 | −0.1476 (3) | 0.25666 (16) | 0.68892 (7) | 0.0250 (4) | |
H26 | −0.2644 | 0.2353 | 0.6762 | 0.030* | |
C27 | −0.0726 (2) | 0.36052 (16) | 0.67463 (6) | 0.0222 (4) | |
H27 | −0.1393 | 0.4111 | 0.6526 | 0.027* | |
C28 | 0.1027 (2) | 0.39369 (15) | 0.69210 (6) | 0.0187 (4) | |
C29 | 0.5376 (3) | 0.61847 (19) | 0.63345 (8) | 0.0317 (4) | |
H29A | 0.4567 | 0.5819 | 0.6080 | 0.048* | |
H29B | 0.6476 | 0.5714 | 0.6376 | 0.048* | |
H29C | 0.5714 | 0.6960 | 0.6213 | 0.048* | |
C30 | 0.6930 (3) | 0.42942 (18) | 0.79361 (8) | 0.0297 (4) | |
H30A | 0.7212 | 0.3508 | 0.7817 | 0.044* | |
H30B | 0.6085 | 0.4256 | 0.8230 | 0.044* | |
H30C | 0.8055 | 0.4681 | 0.8045 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0290 (7) | 0.0200 (6) | 0.0252 (6) | −0.0041 (6) | −0.0044 (6) | 0.0013 (5) |
O2 | 0.0258 (6) | 0.0266 (7) | 0.0251 (7) | −0.0008 (6) | −0.0095 (6) | 0.0015 (5) |
C1 | 0.0178 (8) | 0.0220 (9) | 0.0195 (8) | −0.0005 (7) | −0.0003 (7) | 0.0025 (7) |
C2 | 0.0220 (9) | 0.0227 (9) | 0.0186 (8) | 0.0009 (8) | −0.0026 (7) | 0.0029 (7) |
C3 | 0.0175 (8) | 0.0227 (9) | 0.0189 (8) | −0.0013 (7) | 0.0002 (7) | 0.0006 (7) |
C4 | 0.0225 (8) | 0.0208 (9) | 0.0187 (8) | 0.0006 (7) | −0.0008 (7) | 0.0008 (7) |
C5 | 0.0182 (8) | 0.0218 (9) | 0.0188 (8) | −0.0006 (7) | 0.0002 (7) | 0.0022 (7) |
C6 | 0.0214 (8) | 0.0184 (8) | 0.0212 (8) | 0.0014 (7) | −0.0005 (7) | −0.0004 (7) |
C7 | 0.0167 (8) | 0.0206 (9) | 0.0229 (9) | −0.0004 (7) | −0.0033 (7) | 0.0032 (7) |
C8 | 0.0244 (9) | 0.0224 (9) | 0.0226 (9) | 0.0014 (8) | −0.0031 (7) | 0.0023 (7) |
C9 | 0.0281 (10) | 0.0264 (10) | 0.0283 (10) | 0.0029 (8) | −0.0048 (8) | −0.0039 (8) |
C10 | 0.0294 (10) | 0.0193 (9) | 0.0420 (11) | 0.0030 (8) | −0.0075 (9) | 0.0002 (8) |
C11 | 0.0322 (10) | 0.0247 (10) | 0.0336 (10) | −0.0016 (9) | −0.0049 (9) | 0.0108 (8) |
C12 | 0.0250 (9) | 0.0269 (10) | 0.0239 (9) | −0.0012 (8) | −0.0017 (8) | 0.0027 (7) |
C13 | 0.0198 (8) | 0.0220 (9) | 0.0174 (8) | −0.0025 (7) | 0.0010 (7) | 0.0013 (7) |
C14 | 0.0258 (9) | 0.0248 (9) | 0.0215 (9) | 0.0000 (8) | −0.0017 (7) | 0.0013 (7) |
C15 | 0.0312 (10) | 0.0309 (10) | 0.0201 (9) | −0.0032 (8) | −0.0048 (8) | −0.0002 (8) |
C16 | 0.0294 (10) | 0.0253 (9) | 0.0211 (9) | −0.0052 (8) | 0.0031 (8) | −0.0043 (7) |
C17 | 0.0251 (9) | 0.0227 (9) | 0.0252 (9) | 0.0000 (8) | 0.0026 (8) | −0.0002 (7) |
C18 | 0.0249 (9) | 0.0250 (9) | 0.0189 (9) | 0.0002 (8) | −0.0010 (7) | 0.0015 (7) |
C19 | 0.0240 (9) | 0.0186 (9) | 0.0155 (8) | 0.0026 (7) | 0.0000 (7) | −0.0027 (7) |
C20 | 0.0251 (9) | 0.0187 (9) | 0.0179 (8) | 0.0016 (8) | 0.0005 (7) | −0.0025 (7) |
C21 | 0.0228 (9) | 0.0235 (9) | 0.0170 (8) | 0.0039 (7) | −0.0025 (7) | −0.0038 (7) |
C22 | 0.0257 (9) | 0.0227 (9) | 0.0164 (8) | 0.0047 (7) | −0.0025 (7) | 0.0001 (7) |
C23 | 0.0243 (9) | 0.0207 (9) | 0.0145 (8) | 0.0031 (7) | 0.0019 (7) | −0.0016 (7) |
C24 | 0.0295 (10) | 0.0232 (9) | 0.0172 (8) | 0.0031 (8) | 0.0007 (7) | 0.0007 (7) |
C25 | 0.0317 (10) | 0.0233 (9) | 0.0210 (9) | −0.0039 (8) | 0.0044 (8) | 0.0011 (7) |
C26 | 0.0236 (9) | 0.0295 (10) | 0.0219 (9) | −0.0030 (8) | 0.0000 (8) | −0.0008 (7) |
C27 | 0.0237 (9) | 0.0248 (9) | 0.0182 (8) | 0.0027 (8) | 0.0000 (7) | 0.0005 (7) |
C28 | 0.0219 (8) | 0.0195 (8) | 0.0148 (8) | 0.0021 (7) | 0.0016 (7) | −0.0019 (6) |
C29 | 0.0296 (10) | 0.0336 (11) | 0.0320 (10) | −0.0052 (9) | 0.0038 (9) | 0.0054 (9) |
C30 | 0.0308 (10) | 0.0321 (11) | 0.0261 (10) | 0.0024 (9) | −0.0096 (9) | −0.0006 (8) |
O1—C20 | 1.383 (2) | C14—C15 | 1.389 (3) |
O1—C29 | 1.439 (2) | C15—H15 | 0.9500 |
O2—C21 | 1.357 (2) | C15—C16 | 1.385 (3) |
O2—C30 | 1.436 (2) | C16—H16 | 0.9500 |
C1—C2 | 1.357 (2) | C16—C17 | 1.389 (3) |
C1—C5 | 1.489 (2) | C17—H17 | 0.9500 |
C1—C7 | 1.475 (2) | C17—C18 | 1.382 (3) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C2—C3 | 1.475 (2) | C19—C20 | 1.375 (2) |
C3—C4 | 1.354 (2) | C19—C28 | 1.443 (2) |
C3—C13 | 1.469 (2) | C20—C21 | 1.422 (2) |
C4—H4 | 0.9500 | C21—C22 | 1.372 (3) |
C4—C5 | 1.455 (2) | C22—H22 | 0.9500 |
C5—C6 | 1.351 (2) | C22—C23 | 1.418 (3) |
C6—H6 | 0.9500 | C23—C24 | 1.417 (3) |
C6—C19 | 1.476 (2) | C23—C28 | 1.425 (2) |
C7—C8 | 1.402 (2) | C24—H24 | 0.9500 |
C7—C12 | 1.403 (2) | C24—C25 | 1.371 (3) |
C8—H8 | 0.9500 | C25—H25 | 0.9500 |
C8—C9 | 1.393 (3) | C25—C26 | 1.408 (3) |
C9—H9 | 0.9500 | C26—H26 | 0.9500 |
C9—C10 | 1.384 (3) | C26—C27 | 1.370 (3) |
C10—H10 | 0.9500 | C27—H27 | 0.9500 |
C10—C11 | 1.387 (3) | C27—C28 | 1.417 (3) |
C11—H11 | 0.9500 | C29—H29A | 0.9800 |
C11—C12 | 1.382 (3) | C29—H29B | 0.9800 |
C12—H12 | 0.9500 | C29—H29C | 0.9800 |
C13—C14 | 1.398 (2) | C30—H30A | 0.9800 |
C13—C18 | 1.402 (3) | C30—H30B | 0.9800 |
C14—H14 | 0.9500 | C30—H30C | 0.9800 |
C20—O1—C29 | 112.90 (14) | C17—C16—H16 | 120.1 |
C21—O2—C30 | 116.64 (15) | C16—C17—H17 | 119.9 |
C2—C1—C5 | 106.64 (15) | C18—C17—C16 | 120.23 (18) |
C2—C1—C7 | 125.79 (16) | C18—C17—H17 | 119.9 |
C7—C1—C5 | 127.55 (15) | C13—C18—H18 | 119.6 |
C1—C2—H2 | 125.0 | C17—C18—C13 | 120.86 (17) |
C1—C2—C3 | 110.03 (15) | C17—C18—H18 | 119.6 |
C3—C2—H2 | 125.0 | C20—C19—C6 | 116.56 (16) |
C4—C3—C2 | 107.90 (15) | C20—C19—C28 | 119.35 (16) |
C4—C3—C13 | 126.85 (17) | C28—C19—C6 | 124.01 (16) |
C13—C3—C2 | 125.22 (15) | O1—C20—C21 | 118.28 (16) |
C3—C4—H4 | 125.5 | C19—C20—O1 | 119.31 (16) |
C3—C4—C5 | 109.07 (16) | C19—C20—C21 | 122.39 (17) |
C5—C4—H4 | 125.5 | O2—C21—C20 | 115.38 (16) |
C4—C5—C1 | 106.34 (14) | O2—C21—C22 | 125.74 (16) |
C6—C5—C1 | 127.15 (16) | C22—C21—C20 | 118.88 (17) |
C6—C5—C4 | 126.27 (16) | C21—C22—H22 | 119.6 |
C5—C6—H6 | 116.4 | C21—C22—C23 | 120.82 (16) |
C5—C6—C19 | 127.22 (16) | C23—C22—H22 | 119.6 |
C19—C6—H6 | 116.4 | C22—C23—C28 | 120.52 (16) |
C8—C7—C1 | 122.72 (16) | C24—C23—C22 | 120.26 (17) |
C8—C7—C12 | 117.49 (16) | C24—C23—C28 | 119.22 (17) |
C12—C7—C1 | 119.75 (16) | C23—C24—H24 | 119.6 |
C7—C8—H8 | 119.5 | C25—C24—C23 | 120.73 (18) |
C9—C8—C7 | 120.99 (17) | C25—C24—H24 | 119.6 |
C9—C8—H8 | 119.5 | C24—C25—H25 | 119.9 |
C8—C9—H9 | 119.8 | C24—C25—C26 | 120.15 (18) |
C10—C9—C8 | 120.40 (18) | C26—C25—H25 | 119.9 |
C10—C9—H9 | 119.8 | C25—C26—H26 | 119.8 |
C9—C10—H10 | 120.3 | C27—C26—C25 | 120.37 (18) |
C9—C10—C11 | 119.30 (17) | C27—C26—H26 | 119.8 |
C11—C10—H10 | 120.3 | C26—C27—H27 | 119.4 |
C10—C11—H11 | 119.7 | C26—C27—C28 | 121.11 (17) |
C12—C11—C10 | 120.59 (18) | C28—C27—H27 | 119.4 |
C12—C11—H11 | 119.7 | C23—C28—C19 | 117.96 (16) |
C7—C12—H12 | 119.4 | C27—C28—C19 | 123.74 (16) |
C11—C12—C7 | 121.22 (17) | C27—C28—C23 | 118.30 (16) |
C11—C12—H12 | 119.4 | O1—C29—H29A | 109.5 |
C14—C13—C3 | 121.39 (16) | O1—C29—H29B | 109.5 |
C14—C13—C18 | 118.22 (16) | O1—C29—H29C | 109.5 |
C18—C13—C3 | 120.38 (16) | H29A—C29—H29B | 109.5 |
C13—C14—H14 | 119.6 | H29A—C29—H29C | 109.5 |
C15—C14—C13 | 120.73 (17) | H29B—C29—H29C | 109.5 |
C15—C14—H14 | 119.6 | O2—C30—H30A | 109.5 |
C14—C15—H15 | 119.9 | O2—C30—H30B | 109.5 |
C16—C15—C14 | 120.21 (18) | O2—C30—H30C | 109.5 |
C16—C15—H15 | 119.9 | H30A—C30—H30B | 109.5 |
C15—C16—H16 | 120.1 | H30A—C30—H30C | 109.5 |
C15—C16—C17 | 119.73 (17) | H30B—C30—H30C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O1i | 0.95 | 2.50 | 3.429 (2) | 164 |
C24—H24···O2i | 0.95 | 2.53 | 3.241 (2) | 131 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
1 | 2 | |
C1—C2 | 1.3577 (13) | 1.357 (2) |
C1—C5 | 1.4774 (13) | 1.489 (2) |
C2—C3 | 1.4699 (13) | 1.475 (2) |
C3—C4 | 1.3621 (13) | 1.354 (2) |
C4—C5 | 1.4538 (13) | 1.455 (2) |
C5—C6 | 1.3520 (13) | 1.351 (2) |
C1—C7 | 1.4721 (13) | 1.475 (2) |
C3—13 | 1.4704 (13) | 1.469 (2) |
C6—C19 | 1.4570 (13) | 1.476 (2) |
C2—C1—C5 | 107.36 (8) | 106.64 (15) |
C1—C2—C3 | 109.71 (8) | 110.03 (15) |
C2—C3—C4 | 107.70 (8) | 107.90 (15) |
C3—C4—C5 | 109.12 (8) | 109.07 (16) |
C4—C5—C1 | 106.08 (8) | 106.34 (14) |
C4—C5—C6 | 126.91 (9) | 126.27 (16) |
C1—C5—C6 | 126.72 (9) | 127.15 (16) |
Funding information
Funding for this research was provided by: Air Force Office of Scientific Research; National Research Council (award to LCB).
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