research communications
and Hirshfield analysis of the 4-(dimethylamino)pyridine adduct of 4-methoxyphenylborane
aDepartment of Chemistry, Biochemistry, and Physics, Eastern Washington, University, Cheney, WA 99004, USA, and bDepartment of Chemistry and Biochemistry, CAMCOR, University of Oregon, Eugene, OR 97403, USA
*Correspondence e-mail: eabbey@ewu.edu
The title compound [systematic name: 4-(dimethylamino)pyridine–4-methoxyphenylborane (1/1)], C14H19BN2O, contains two independent molecules in the Both molecules exhibit coplanar, mostly sp2-hybridized methoxy and dimethylamino substituents on their respective aromatic rings, consistent with π-donation into the aromatic systems. The B—H groups exhibit an intramolecular close contact with a C—H group of the pyridine ring, which may be evidence of electrostatic attraction between the hydridic B—H and the electropositive aromatic C—H. There appears to be weak C—H⋯π(arene) interactions between two of the H atoms of an aminomethyl group and the methoxy-substituted benzene ring of the other independent molecule, and another C—H⋯π (arene) interaction between one of the pyridine ring H atoms and the same benzene ring.
Keywords: crystal structure; hydrogen bonding; zwitterions; Hirshfield analysis.
CCDC reference: 1580559
1. Chemical context
Monoorganoboranes (RBH2) have been the focus of chemical research for over fifty years, most notably for their use in the indispensable hydroboration reaction, which permits reduction of and others (Brown & Krishnamurthy, 1979; Crudden & Edwards, 2003.) Such are often isolated as their adducts, in which the base donates a lone pair into the vacant p orbital of the sp2 borane. Among the most common class of Lewis bases for the formation of borane adducts are Amine are widely used as hydroboration reagents (Clay & Vedejs, 2005), precursors for borenium cation synthesis (De Vries et al., 2012), frustrated Lewis pairs (Stephan, 2015), and have been investigated as hydrogen-storage materials (Campbell et al., 2010). We have synthesized the zwitterionic title compound by hydride removal from sodium 4-methoxyphenylborohydride with chlorotrimethylsilane in the presence of 4-dimethylaminopyridine. This compound is slightly unusual, as examples of monoorganoboranes with heteroatoms on the organic substitituent are limited.
2. Structural commentary
The and 2) with only slightly different geometric features (Fig. 3). In both molecules, the boron atom appears to be sp3 hybridized [C1—B1—N1 = 110.8 (1) and C1′—B1′—N1′ = 111.0 (1)°] . The B1—C1 and B1′—C1′ distances [1.608 (2) and 1.611 (2) Å, respectively] are consistent with a formal C—B single bond. The oxygen atom of both methoxy groups appears to be mostly sp2 hybridized, [C7—O1—C4 = 117.3 (1) and C7′—O1′—C4′ = 117.4 (1)°] and is close to coplanar with the phenyl ring [torsion angles C7—O1—C4—C3 = −7.4 (2) and C7′—O1′—C4′—C3′ = −7.1 (2)°], consistent with π-donation into the phenyl ring.
contains two independent molecules (Figs. 1The geometries of the 4-(dimethylamino)pyridine (DMAP) fragment of both molecules is similar to other structures of DMAP–borane adducts. The nitrogen atom of the dimethylamino fragment appears to be sp2 hybridized [torsion angles C13—N2—C10 = 121.0 (1)° and C13′—N2′—C10′ = 122.2 (1)°] and is close to coplanar [torsion angles C13—N2—C10—C11 = 2.4 (2) and C13′—N2′—C10′—C11′ = 3.4 (1)°] consistent with π-donation into the pyridine ring.
The B1—N1 and B1′—N1′ distances [1.597 (2) and 1.595 (2) Å, respectively] are consistent with formal N—B single bonds, and are within the range observed for other DMAP–borane adducts (see Database survey). Interestingly, the B—H atoms exhibit intramolecular close contacts with the C—H atoms of the pyridine ring [H12⋯H2B = 2.26 (3) and H12′⋯H2B′ = 2.27 (3) Å] and are close to coplanar [torsion angles H2B—B1—N1—C12 = 4(1) and H2B—B1—N1—C12 = 16 (1)°], which may be evidence of electrostatic interactions between the hydridic B—H atoms and electropositive aromatic C—H atoms, and is observed in other DMAP–borane adducts (see Database Survey). The planes of the pyridine rings and the benzene rings are almost normal to one another [the dihedral angle between the C1–C6 and C8–C12/N1 rings is 73.14 (7)° and that between the C1′–C6′ and C8′–C12′/N1′ rings is 74.15 (7)°]. Perhaps the most significant difference between the two molecules is the 9.0° difference in the torsion angle about the B—N bond [C1—B1—N1—C8 = −63.9 (2) while C1′—B1′—N1′—C8′ = −72.9 (2)°] (Fig. 3).
3. Supramolecular features
The molecules within the π (arene) interactions between two of the hydrogen atoms of the aminomethyl group and the methoxyphenyl group of a neighboring molecule (see Table 1) as well as a C—H⋯π(arene) interaction between one of the pyridine hydrogen atoms and the same methoxyphenyl ring (Fig. 4).
exhibit weak C—H⋯
|
4. Hirshfield analysis
The weak intermolecular interactions of the title compound were explored by Hirshfield analysis. Hirshfield surfaces were generated using Crystal Explorer 3.1 (McKinnon et al., 2007; Spackman & Jayatilaka, 2009). The space within a crystal is partitioned so that the ratio of promolecule to procrystal is equal to 0.5, generating continuous surfaces that permit the visualization of weak interactions. The dnorm values illustrate whether the intermolecular contact is shorter or longer than the van der Waals radii. Red areas of the Hirshfield surface indicate negative dnorm values contacts closer than the van der Waals radii. This analysis lends further support to the weak C—H⋯π (arene) interactions described in the previous section (Fig. 5.)
5. Database survey
A search of the Cambridge Structural Database (Version 5.37, update February 2017; Groom et al., 2016) for DMAP–borane adducts yielded only two structures: VOGJEI (Chu, et al., 2014) and JUDQAA (Lesley et al., 1998). A search for phenyl-based monoorganoborane–amine adducts (Ph–BH2–NR3) yielded four structures: UTOZEJ (Hubner et al., 2012), BEXQOM (Ménard & Stephan, 2013), EPOYAK (Franz et al., 2011), and GEBNAE (Jacobs et al., 2012). In all four of these structures, the B—N bonds are approximately perpendicular to the plane of the arene rings. In all six cases, the boron atom is tetrahedral and displays structural features consistent with sp3 Additionally, the C—B and B—N bonds are all within the range for formal C—B and C—N single bonds.
6. Synthesis and crystallization
In a nitrogen-filled via syringe. The reaction was allowed to come to 295 K and was stirred for 1 h. The solvent was then removed in vacuo and the residue was washed with anhydrous diethyl ether (4 mL), followed by extraction with anhydrous dichloromethane (4 mL). The extract was filtered through a 0.45 µm PTFE syringe filter. The solvent was again removed in vacuo to afford a white solid (51 mg, 37%). Crystals suitable for X-ray diffraction were grown by diffusion of pentane into a concentrated solution of the title compound in anhydrous dichloromethane.
sodium 4-methoxyphenylborohydride (97mg, 0.67 mmol) and 4-dimethylaminopyridine (82 mg, 0.67 mmol) were combined in a 20 mL vial containing a stir bar and dissolved in anhydrous THF (4 mL). The solution was cooled to 247 K in the freezer and chlorotrimethylsilane (73 mg, 0.67 mmol) was added dropwise1H NMR (500 MHz, CDCl3) δ (ppm): 8.12 (d, 2H, J = 7 Hz), 7.23 (d, 2 H, J = 8 Hz), 6.80 (d, 2H, J = 8.5 Hz), 6.52 (d, 2H, J = 8 Hz), 3.78 (s, 3H), 3.11 (s, 6H). 13C NMR (126 MHz, CDCl3) δ (ppm): 157.3, 154.9, 146.7, 145.0 (br s), 134.5, 122.9, 106.5, 55.0, 39.5. 11B NMR (160 MHz, CDCl3) δ (ppm): −5.0 (br, s). FTIR (ATR, cm−1): 3012, 2952, 2923, 2853, 2610, 2346, 2288, 2227, 1634, 1548, 1442, 1418, 1392, 1237, 1223, 1161, 1076, 1031, 811, 797, 548, 515.
7. Refinement
Crystal data, data collection and structure . H atoms were refined in calculated positions (C—H = 0.95 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2eq(C) for other H atoms. The B-bound H atoms were located in a difference-Fourier map and freely refined. Methyl H atoms were refined without restrictions on rotation around the C—C bonds, HFIX 138 in SHELXL (Sheldrick, 2015).
details are summarized in Table 2Supporting information
CCDC reference: 1580559
https://doi.org/10.1107/S2056989017015171/lh5853sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015171/lh5853Isup2.hkl
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C14H19BN2O | Dx = 1.185 Mg m−3 |
Mr = 242.12 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pbca | Cell parameters from 6122 reflections |
a = 12.3538 (6) Å | θ = 3.8–66.5° |
b = 18.7727 (10) Å | µ = 0.58 mm−1 |
c = 23.4056 (12) Å | T = 173 K |
V = 5428.1 (5) Å3 | Cut-block, colorless |
Z = 16 | 0.14 × 0.09 × 0.07 mm |
F(000) = 2080 |
Bruker APEXII CCD diffractometer | 3948 reflections with I > 2σ(I) |
Radiation source: Incoatec IµS | Rint = 0.063 |
φ and ω scans | θmax = 66.6°, θmin = 3.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −14→14 |
Tmin = 0.695, Tmax = 0.753 | k = −22→21 |
46022 measured reflections | l = −27→27 |
4800 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0934P)2 + 0.2472P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
4800 reflections | Δρmax = 0.22 e Å−3 |
353 parameters | Δρmin = −0.22 e Å−3 |
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 | ||
B1 | 1.01984 (15) | 0.31745 (11) | 0.41477 (9) | 0.0427 (4) | |
O1 | 0.94372 (10) | 0.19525 (7) | 0.63937 (5) | 0.0486 (3) | |
N1 | 0.91495 (10) | 0.31876 (7) | 0.37491 (5) | 0.0350 (3) | |
N2 | 0.64797 (11) | 0.31846 (7) | 0.26602 (6) | 0.0409 (3) | |
C1 | 0.99199 (12) | 0.28402 (8) | 0.47629 (6) | 0.0336 (3) | |
C2 | 0.88854 (12) | 0.27979 (8) | 0.50007 (7) | 0.0349 (3) | |
H2A | 0.8290 | 0.2968 | 0.4783 | 0.042* | |
C3 | 0.86858 (12) | 0.25193 (8) | 0.55404 (7) | 0.0367 (3) | |
H3A | 0.7969 | 0.2504 | 0.5686 | 0.044* | |
C4 | 0.95416 (12) | 0.22634 (8) | 0.58646 (6) | 0.0365 (3) | |
C5 | 1.05847 (12) | 0.23022 (9) | 0.56465 (7) | 0.0386 (4) | |
H5A | 1.1178 | 0.2135 | 0.5867 | 0.046* | |
C6 | 1.07595 (12) | 0.25838 (8) | 0.51094 (7) | 0.0364 (3) | |
H6A | 1.1480 | 0.2605 | 0.4969 | 0.044* | |
C7 | 0.84022 (17) | 0.19686 (13) | 0.66503 (8) | 0.0623 (5) | |
H7A | 0.8163 (7) | 0.2472 (7) | 0.6695 (7) | 0.093* | |
H7B | 0.8437 (4) | 0.1737 (9) | 0.7032 (6) | 0.093* | |
H7C | 0.7877 (8) | 0.1708 (9) | 0.6404 (5) | 0.093* | |
C8 | 0.86637 (13) | 0.25774 (8) | 0.35835 (7) | 0.0384 (4) | |
H8A | 0.8952 | 0.2140 | 0.3720 | 0.046* | |
C9 | 0.77855 (12) | 0.25513 (8) | 0.32330 (7) | 0.0372 (3) | |
H9A | 0.7479 | 0.2104 | 0.3133 | 0.045* | |
C10 | 0.73265 (12) | 0.31892 (8) | 0.30166 (6) | 0.0331 (3) | |
C11 | 0.78395 (13) | 0.38231 (8) | 0.31977 (7) | 0.0365 (3) | |
H11A | 0.7572 | 0.4271 | 0.3072 | 0.044* | |
C12 | 0.87174 (13) | 0.37956 (8) | 0.35519 (6) | 0.0365 (3) | |
H12A | 0.9041 | 0.4232 | 0.3665 | 0.044* | |
C13 | 0.59485 (15) | 0.25190 (10) | 0.25018 (8) | 0.0502 (4) | |
H13A | 0.6465 (8) | 0.2208 (5) | 0.2318 (6) | 0.075* | |
H13B | 0.5359 (11) | 0.26183 (17) | 0.2242 (6) | 0.075* | |
H13C | 0.5669 (11) | 0.2290 (5) | 0.2841 (5) | 0.075* | |
C14 | 0.60151 (17) | 0.38459 (11) | 0.24483 (9) | 0.0582 (5) | |
H14A | 0.5688 (13) | 0.4106 (6) | 0.2764 (5) | 0.087* | |
H14B | 0.5465 (13) | 0.37391 (18) | 0.2163 (7) | 0.087* | |
H14C | 0.6582 (9) | 0.4135 (6) | 0.2276 (7) | 0.087* | |
B1' | 0.69503 (16) | 0.06081 (12) | 0.15670 (9) | 0.0453 (5) | |
O1' | 0.60935 (10) | 0.06495 (7) | 0.40101 (5) | 0.0465 (3) | |
N1' | 0.59005 (11) | 0.04914 (7) | 0.11816 (5) | 0.0376 (3) | |
N2' | 0.31932 (10) | 0.01508 (7) | 0.01478 (6) | 0.0381 (3) | |
C1' | 0.66395 (12) | 0.06221 (8) | 0.22354 (7) | 0.0353 (3) | |
C2' | 0.55974 (13) | 0.05774 (9) | 0.24570 (7) | 0.0390 (4) | |
H2'A | 0.5010 | 0.0533 | 0.2197 | 0.047* | |
C3' | 0.53692 (13) | 0.05950 (9) | 0.30416 (7) | 0.0391 (4) | |
H3'A | 0.4642 | 0.0567 | 0.3172 | 0.047* | |
C4' | 0.62082 (13) | 0.06528 (8) | 0.34280 (7) | 0.0355 (3) | |
C5' | 0.72647 (12) | 0.07031 (8) | 0.32248 (7) | 0.0375 (4) | |
H5'A | 0.7850 | 0.0747 | 0.3486 | 0.045* | |
C6' | 0.74621 (12) | 0.06892 (8) | 0.26434 (7) | 0.0365 (4) | |
H6'A | 0.8189 | 0.0727 | 0.2515 | 0.044* | |
C7' | 0.50222 (15) | 0.06648 (10) | 0.42327 (8) | 0.0505 (4) | |
H7'1 | 0.4633 (7) | 0.1089 (7) | 0.4080 (6) | 0.076* | |
H7'2 | 0.50509 (15) | 0.0693 (8) | 0.4658 (6) | 0.076* | |
H7'3 | 0.4632 (7) | 0.0223 (7) | 0.4117 (6) | 0.076* | |
C8' | 0.54070 (13) | −0.01494 (9) | 0.11568 (7) | 0.0389 (4) | |
H8'A | 0.5701 | −0.0528 | 0.1376 | 0.047* | |
C9' | 0.45100 (13) | −0.02840 (8) | 0.08343 (7) | 0.0370 (3) | |
H9'A | 0.4193 | −0.0745 | 0.0839 | 0.044* | |
C10' | 0.40477 (12) | 0.02603 (8) | 0.04920 (6) | 0.0335 (3) | |
C11' | 0.45656 (13) | 0.09326 (8) | 0.05317 (6) | 0.0360 (3) | |
H11B | 0.4290 | 0.1326 | 0.0322 | 0.043* | |
C12' | 0.54561 (13) | 0.10182 (8) | 0.08691 (7) | 0.0372 (3) | |
H12B | 0.5782 | 0.1476 | 0.0885 | 0.045* | |
C13' | 0.26225 (14) | −0.05283 (9) | 0.01282 (8) | 0.0450 (4) | |
H13D | 0.3125 (7) | −0.0908 (5) | 0.0187 (6) | 0.068* | |
H13E | 0.2285 (10) | −0.0583 (4) | −0.0236 (5) | 0.068* | |
H13F | 0.2083 (10) | −0.0539 (3) | 0.0421 (5) | 0.068* | |
C14' | 0.26866 (14) | 0.07399 (10) | −0.01557 (8) | 0.0459 (4) | |
H14D | 0.2354 (11) | 0.1068 (6) | 0.0122 (4) | 0.069* | |
H14E | 0.2125 (11) | 0.0554 (2) | −0.0414 (5) | 0.069* | |
H14F | 0.3238 (7) | 0.0996 (6) | −0.0380 (5) | 0.069* | |
H1'B | 0.7533 (16) | 0.0147 (10) | 0.1468 (8) | 0.048 (5)* | |
H1B | 1.0840 (16) | 0.2841 (11) | 0.3930 (8) | 0.051 (5)* | |
H2'B | 0.7314 (16) | 0.1141 (10) | 0.1398 (9) | 0.052 (5)* | |
H2B | 1.0475 (17) | 0.3752 (11) | 0.4179 (9) | 0.056 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.0358 (9) | 0.0501 (11) | 0.0424 (10) | −0.0072 (8) | −0.0031 (8) | 0.0077 (8) |
O1 | 0.0447 (7) | 0.0665 (8) | 0.0345 (6) | 0.0031 (6) | 0.0016 (5) | 0.0079 (5) |
N1 | 0.0361 (7) | 0.0375 (7) | 0.0315 (7) | −0.0030 (5) | 0.0009 (5) | 0.0049 (5) |
N2 | 0.0397 (7) | 0.0423 (8) | 0.0406 (7) | 0.0009 (6) | −0.0056 (6) | −0.0007 (6) |
C1 | 0.0324 (7) | 0.0329 (7) | 0.0354 (8) | −0.0015 (6) | −0.0026 (6) | −0.0015 (6) |
C2 | 0.0303 (7) | 0.0369 (8) | 0.0375 (8) | 0.0020 (6) | −0.0049 (6) | 0.0006 (6) |
C3 | 0.0290 (7) | 0.0423 (8) | 0.0386 (8) | 0.0001 (6) | 0.0019 (6) | −0.0028 (6) |
C4 | 0.0390 (8) | 0.0407 (8) | 0.0298 (7) | 0.0001 (6) | −0.0022 (6) | −0.0017 (6) |
C5 | 0.0335 (8) | 0.0454 (9) | 0.0370 (8) | 0.0026 (6) | −0.0075 (6) | 0.0008 (7) |
C6 | 0.0273 (7) | 0.0431 (8) | 0.0387 (8) | −0.0005 (6) | 0.0005 (6) | −0.0017 (6) |
C7 | 0.0574 (12) | 0.0904 (15) | 0.0391 (10) | 0.0067 (10) | 0.0129 (8) | 0.0114 (10) |
C8 | 0.0417 (8) | 0.0327 (8) | 0.0407 (8) | −0.0009 (6) | −0.0021 (7) | 0.0070 (6) |
C9 | 0.0418 (8) | 0.0314 (7) | 0.0385 (8) | −0.0039 (6) | −0.0003 (7) | 0.0005 (6) |
C10 | 0.0337 (7) | 0.0379 (8) | 0.0277 (7) | 0.0013 (6) | 0.0039 (6) | −0.0001 (6) |
C11 | 0.0435 (8) | 0.0324 (8) | 0.0336 (8) | 0.0030 (6) | 0.0000 (6) | −0.0006 (6) |
C12 | 0.0434 (8) | 0.0334 (8) | 0.0328 (8) | −0.0032 (6) | 0.0018 (6) | 0.0000 (6) |
C13 | 0.0459 (9) | 0.0540 (10) | 0.0507 (10) | −0.0061 (8) | −0.0117 (8) | −0.0059 (8) |
C14 | 0.0568 (12) | 0.0560 (11) | 0.0618 (12) | 0.0110 (9) | −0.0197 (9) | 0.0004 (9) |
B1' | 0.0333 (9) | 0.0635 (12) | 0.0392 (10) | −0.0031 (8) | 0.0021 (8) | 0.0000 (8) |
O1' | 0.0467 (7) | 0.0583 (7) | 0.0345 (6) | 0.0036 (5) | −0.0030 (5) | −0.0021 (5) |
N1' | 0.0349 (7) | 0.0465 (8) | 0.0315 (7) | −0.0003 (5) | 0.0042 (5) | −0.0018 (5) |
N2' | 0.0345 (7) | 0.0418 (7) | 0.0378 (7) | −0.0006 (5) | −0.0013 (5) | 0.0025 (5) |
C1' | 0.0328 (8) | 0.0339 (7) | 0.0393 (8) | −0.0006 (6) | −0.0021 (6) | 0.0000 (6) |
C2' | 0.0308 (8) | 0.0505 (9) | 0.0358 (8) | −0.0013 (6) | −0.0052 (6) | −0.0034 (7) |
C3' | 0.0300 (8) | 0.0469 (9) | 0.0403 (9) | −0.0005 (6) | 0.0006 (6) | −0.0014 (7) |
C4' | 0.0398 (8) | 0.0323 (7) | 0.0345 (8) | 0.0018 (6) | −0.0025 (6) | −0.0024 (6) |
C5' | 0.0351 (8) | 0.0343 (8) | 0.0431 (9) | 0.0009 (6) | −0.0108 (7) | −0.0014 (6) |
C6' | 0.0291 (7) | 0.0354 (8) | 0.0449 (9) | 0.0008 (6) | −0.0013 (6) | −0.0001 (6) |
C7' | 0.0538 (11) | 0.0577 (11) | 0.0399 (9) | 0.0058 (8) | 0.0071 (8) | −0.0059 (8) |
C8' | 0.0408 (8) | 0.0427 (8) | 0.0333 (8) | 0.0051 (7) | 0.0034 (6) | 0.0034 (6) |
C9' | 0.0402 (8) | 0.0365 (8) | 0.0345 (8) | −0.0002 (6) | 0.0049 (6) | 0.0004 (6) |
C10' | 0.0329 (7) | 0.0383 (8) | 0.0292 (7) | 0.0024 (6) | 0.0064 (6) | −0.0022 (6) |
C11' | 0.0375 (8) | 0.0358 (8) | 0.0346 (8) | 0.0037 (6) | 0.0041 (6) | 0.0007 (6) |
C12' | 0.0386 (8) | 0.0375 (8) | 0.0354 (8) | −0.0011 (6) | 0.0067 (6) | −0.0026 (6) |
C13' | 0.0406 (9) | 0.0491 (9) | 0.0454 (9) | −0.0092 (7) | 0.0018 (7) | −0.0001 (7) |
C14' | 0.0403 (9) | 0.0520 (10) | 0.0455 (10) | 0.0028 (7) | −0.0049 (7) | 0.0069 (7) |
B1—N1 | 1.597 (2) | B1'—N1' | 1.595 (2) |
B1—C1 | 1.608 (2) | B1'—C1' | 1.611 (2) |
B1—H1B | 1.13 (2) | B1'—H1'B | 1.150 (19) |
B1—H2B | 1.14 (2) | B1'—H2'B | 1.166 (19) |
O1—C4 | 1.3752 (19) | O1'—C4' | 1.370 (2) |
O1—C7 | 1.413 (2) | O1'—C7' | 1.423 (2) |
N1—C12 | 1.342 (2) | N1'—C12' | 1.347 (2) |
N1—C8 | 1.350 (2) | N1'—C8' | 1.350 (2) |
N2—C10 | 1.338 (2) | N2'—C10' | 1.344 (2) |
N2—C14 | 1.455 (2) | N2'—C14' | 1.456 (2) |
N2—C13 | 1.459 (2) | N2'—C13' | 1.458 (2) |
C1—C2 | 1.396 (2) | C1'—C2' | 1.390 (2) |
C1—C6 | 1.402 (2) | C1'—C6' | 1.400 (2) |
C2—C3 | 1.389 (2) | C2'—C3' | 1.397 (2) |
C2—H2A | 0.9500 | C2'—H2'A | 0.9500 |
C3—C4 | 1.387 (2) | C3'—C4' | 1.380 (2) |
C3—H3A | 0.9500 | C3'—H3'A | 0.9500 |
C4—C5 | 1.388 (2) | C4'—C5' | 1.392 (2) |
C5—C6 | 1.381 (2) | C5'—C6' | 1.383 (2) |
C5—H5A | 0.9500 | C5'—H5'A | 0.9500 |
C6—H6A | 0.9500 | C6'—H6'A | 0.9500 |
C7—H7A | 0.996 (14) | C7'—H7'1 | 0.996 (14) |
C7—H7B | 0.996 (14) | C7'—H7'2 | 0.996 (14) |
C7—H7C | 0.996 (14) | C7'—H7'3 | 0.996 (14) |
C8—C9 | 1.361 (2) | C8'—C9' | 1.364 (2) |
C8—H8A | 0.9500 | C8'—H8'A | 0.9500 |
C9—C10 | 1.419 (2) | C9'—C10' | 1.419 (2) |
C9—H9A | 0.9500 | C9'—H9'A | 0.9500 |
C10—C11 | 1.413 (2) | C10'—C11' | 1.418 (2) |
C11—C12 | 1.366 (2) | C11'—C12' | 1.364 (2) |
C11—H11A | 0.9500 | C11'—H11B | 0.9500 |
C12—H12A | 0.9500 | C12'—H12B | 0.9500 |
C13—H13A | 0.967 (13) | C13'—H13D | 0.955 (12) |
C13—H13B | 0.967 (13) | C13'—H13E | 0.955 (12) |
C13—H13C | 0.967 (13) | C13'—H13F | 0.955 (12) |
C14—H14A | 0.973 (15) | C14'—H14D | 0.985 (12) |
C14—H14B | 0.973 (15) | C14'—H14E | 0.985 (12) |
C14—H14C | 0.973 (15) | C14'—H14F | 0.985 (12) |
N1—B1—C1 | 110.83 (13) | N1'—B1'—C1' | 110.96 (13) |
N1—B1—H1B | 108.2 (10) | N1'—B1'—H1'B | 107.0 (10) |
C1—B1—H1B | 109.7 (10) | C1'—B1'—H1'B | 110.9 (10) |
N1—B1—H2B | 105.5 (10) | N1'—B1'—H2'B | 103.9 (10) |
C1—B1—H2B | 112.2 (11) | C1'—B1'—H2'B | 114.0 (10) |
H1B—B1—H2B | 110.2 (14) | H1'B—B1'—H2'B | 109.7 (14) |
C4—O1—C7 | 117.30 (14) | C4'—O1'—C7' | 117.41 (13) |
C12—N1—C8 | 116.49 (13) | C12'—N1'—C8' | 116.54 (13) |
C12—N1—B1 | 122.47 (13) | C12'—N1'—B1' | 122.52 (14) |
C8—N1—B1 | 121.02 (13) | C8'—N1'—B1' | 120.93 (14) |
C10—N2—C14 | 121.03 (14) | C10'—N2'—C14' | 120.93 (13) |
C10—N2—C13 | 121.04 (13) | C10'—N2'—C13' | 122.19 (13) |
C14—N2—C13 | 117.81 (14) | C14'—N2'—C13' | 116.18 (14) |
C2—C1—C6 | 115.29 (14) | C2'—C1'—C6' | 115.03 (14) |
C2—C1—B1 | 125.10 (13) | C2'—C1'—B1' | 125.57 (14) |
C6—C1—B1 | 119.59 (14) | C6'—C1'—B1' | 119.39 (14) |
C3—C2—C1 | 123.11 (14) | C1'—C2'—C3' | 123.40 (15) |
C3—C2—H2A | 118.4 | C1'—C2'—H2'A | 118.3 |
C1—C2—H2A | 118.4 | C3'—C2'—H2'A | 118.3 |
C4—C3—C2 | 119.50 (14) | C4'—C3'—C2' | 119.48 (15) |
C4—C3—H3A | 120.2 | C4'—C3'—H3'A | 120.3 |
C2—C3—H3A | 120.2 | C2'—C3'—H3'A | 120.3 |
O1—C4—C3 | 124.62 (14) | O1'—C4'—C3' | 125.02 (15) |
O1—C4—C5 | 116.14 (14) | O1'—C4'—C5' | 115.90 (14) |
C3—C4—C5 | 119.23 (14) | C3'—C4'—C5' | 119.06 (15) |
C6—C5—C4 | 120.01 (14) | C6'—C5'—C4' | 120.00 (14) |
C6—C5—H5A | 120.0 | C6'—C5'—H5'A | 120.0 |
C4—C5—H5A | 120.0 | C4'—C5'—H5'A | 120.0 |
C5—C6—C1 | 122.85 (14) | C5'—C6'—C1' | 123.02 (14) |
C5—C6—H6A | 118.6 | C5'—C6'—H6'A | 118.5 |
C1—C6—H6A | 118.6 | C1'—C6'—H6'A | 118.5 |
O1—C7—H7A | 109.5 | O1'—C7'—H7'1 | 109.5 |
O1—C7—H7B | 109.5 | O1'—C7'—H7'2 | 109.5 |
H7A—C7—H7B | 109.5 | H7'1—C7'—H7'2 | 109.5 |
O1—C7—H7C | 109.5 | O1'—C7'—H7'3 | 109.5 |
H7A—C7—H7C | 109.5 | H7'1—C7'—H7'3 | 109.5 |
H7B—C7—H7C | 109.5 | H7'2—C7'—H7'3 | 109.5 |
N1—C8—C9 | 123.92 (14) | N1'—C8'—C9' | 123.76 (14) |
N1—C8—H8A | 118.0 | N1'—C8'—H8'A | 118.1 |
C9—C8—H8A | 118.0 | C9'—C8'—H8'A | 118.1 |
C8—C9—C10 | 120.23 (14) | C8'—C9'—C10' | 120.40 (14) |
C8—C9—H9A | 119.9 | C8'—C9'—H9'A | 119.8 |
C10—C9—H9A | 119.9 | C10'—C9'—H9'A | 119.8 |
N2—C10—C11 | 122.89 (14) | N2'—C10'—C9' | 123.00 (14) |
N2—C10—C9 | 121.99 (14) | N2'—C10'—C11' | 122.00 (14) |
C11—C10—C9 | 115.11 (14) | C9'—C10'—C11' | 114.99 (14) |
C12—C11—C10 | 120.41 (14) | C12'—C11'—C10' | 120.44 (14) |
C12—C11—H11A | 119.8 | C12'—C11'—H11B | 119.8 |
C10—C11—H11A | 119.8 | C10'—C11'—H11B | 119.8 |
N1—C12—C11 | 123.83 (14) | N1'—C12'—C11' | 123.83 (14) |
N1—C12—H12A | 118.1 | N1'—C12'—H12B | 118.1 |
C11—C12—H12A | 118.1 | C11'—C12'—H12B | 118.1 |
N2—C13—H13A | 109.5 | N2'—C13'—H13D | 109.5 |
N2—C13—H13B | 109.5 | N2'—C13'—H13E | 109.5 |
H13A—C13—H13B | 109.5 | H13D—C13'—H13E | 109.5 |
N2—C13—H13C | 109.5 | N2'—C13'—H13F | 109.5 |
H13A—C13—H13C | 109.5 | H13D—C13'—H13F | 109.5 |
H13B—C13—H13C | 109.5 | H13E—C13'—H13F | 109.5 |
N2—C14—H14A | 109.5 | N2'—C14'—H14D | 109.5 |
N2—C14—H14B | 109.5 | N2'—C14'—H14E | 109.5 |
H14A—C14—H14B | 109.5 | H14D—C14'—H14E | 109.5 |
N2—C14—H14C | 109.5 | N2'—C14'—H14F | 109.5 |
H14A—C14—H14C | 109.5 | H14D—C14'—H14F | 109.5 |
H14B—C14—H14C | 109.5 | H14E—C14'—H14F | 109.5 |
C1—B1—N1—C12 | 117.49 (16) | C1'—B1'—N1'—C12' | 106.68 (17) |
C1—B1—N1—C8 | −63.9 (2) | C1'—B1'—N1'—C8' | −72.92 (19) |
N1—B1—C1—C2 | −21.1 (2) | N1'—B1'—C1'—C2' | −3.2 (2) |
N1—B1—C1—C6 | 160.91 (14) | N1'—B1'—C1'—C6' | 177.29 (14) |
C6—C1—C2—C3 | −0.4 (2) | C6'—C1'—C2'—C3' | −0.2 (2) |
B1—C1—C2—C3 | −178.43 (15) | B1'—C1'—C2'—C3' | −179.71 (16) |
C1—C2—C3—C4 | −0.5 (2) | C1'—C2'—C3'—C4' | −0.6 (3) |
C7—O1—C4—C3 | −7.4 (2) | C7'—O1'—C4'—C3' | −7.1 (2) |
C7—O1—C4—C5 | 173.96 (17) | C7'—O1'—C4'—C5' | 174.38 (14) |
C2—C3—C4—O1 | −177.46 (15) | C2'—C3'—C4'—O1' | −177.51 (15) |
C2—C3—C4—C5 | 1.1 (2) | C2'—C3'—C4'—C5' | 1.0 (2) |
O1—C4—C5—C6 | 177.77 (14) | O1'—C4'—C5'—C6' | 178.10 (13) |
C3—C4—C5—C6 | −0.9 (2) | C3'—C4'—C5'—C6' | −0.5 (2) |
C4—C5—C6—C1 | 0.1 (2) | C4'—C5'—C6'—C1' | −0.3 (2) |
C2—C1—C6—C5 | 0.6 (2) | C2'—C1'—C6'—C5' | 0.6 (2) |
B1—C1—C6—C5 | 178.75 (15) | B1'—C1'—C6'—C5' | −179.77 (15) |
C12—N1—C8—C9 | 0.4 (2) | C12'—N1'—C8'—C9' | 0.6 (2) |
B1—N1—C8—C9 | −178.28 (15) | B1'—N1'—C8'—C9' | −179.78 (14) |
N1—C8—C9—C10 | 0.2 (2) | N1'—C8'—C9'—C10' | 0.9 (2) |
C14—N2—C10—C11 | −1.7 (2) | C14'—N2'—C10'—C9' | 174.39 (14) |
C13—N2—C10—C11 | −177.60 (15) | C13'—N2'—C10'—C9' | 4.4 (2) |
C14—N2—C10—C9 | 179.35 (16) | C14'—N2'—C10'—C11' | −6.6 (2) |
C13—N2—C10—C9 | 3.4 (2) | C13'—N2'—C10'—C11' | −176.65 (14) |
C8—C9—C10—N2 | 178.37 (14) | C8'—C9'—C10'—N2' | 177.12 (14) |
C8—C9—C10—C11 | −0.7 (2) | C8'—C9'—C10'—C11' | −1.9 (2) |
N2—C10—C11—C12 | −178.48 (14) | N2'—C10'—C11'—C12' | −177.51 (14) |
C9—C10—C11—C12 | 0.6 (2) | C9'—C10'—C11'—C12' | 1.5 (2) |
C8—N1—C12—C11 | −0.5 (2) | C8'—N1'—C12'—C11' | −1.0 (2) |
B1—N1—C12—C11 | 178.13 (15) | B1'—N1'—C12'—C11' | 179.36 (14) |
C10—C11—C12—N1 | 0.1 (2) | C10'—C11'—C12'—N1' | −0.1 (2) |
Cg is the centroid of the C1'–C6' ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···Cg | 0.95 | 3.12 | 4.069 (2) | 178 |
C13—H13A···Cg | 0.97 | 3.12 | 3.662 (2) | 112 |
C13—H13C···Cg | 0.97 | 3.23 | 3.662 (2) | 109 |
Funding information
Funding for this research was provided by: Eastern Washington University Faculty Grants for Creative Works.
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