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ISSN: 2414-3146

10-Phenyl-10H-phenoxazine-4,6-diol tetra­hydro­furan monosolvate

aDepartment of Chemistry, Davidson College, Davidson, North Carolina, USA, and bDepartment of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, 19104-6323, USA
*Correspondence e-mail: mitch.anstey@davidson.edu

Edited by S. Parkin, University of Kentucky, USA (Received 28 August 2020; accepted 18 September 2020; online 25 September 2020)

In the crystalline state of the title solvate, C18H13NO3·C4H8O, hydrogen-bonding inter­actions between hydroxyl groups on a phenoxazine backbone and the tetra­hydro­furan solvent are observed that suggest the ability for this compound to act as a chelating ligand. The O⋯O donor–acceptor distances for this hydrogen bonding are 2.7729 (15) and 2.7447 (15) Å. The three-ring backbone of the phenoxazine bends out of planarity by 18.92 (3)°, as computed using mean planes that encompass each half of the three-ring structure, with the central N and O atoms forming the line of flexion. In the crystal, a ππ stacking arrangement exists between inversion-related mol­ecules, with a centroid-to-centroid distance of 3.6355 (11) Å. In the disordered tetra­hydro­furan solvate, all atoms except oxygen were modeled over two positions, with occupancies of 0.511 (8) and 0.489 (8).

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Phenoxazine-based metal complexes have been reported as catalysts in hydro­formyl­ation reactions (van der Veen et al., 2000[Veen, L. A. van der, Keeven, P. H., Schoemaker, G. C., Reek, J. N. H., Kamer, P. C. J., van Leeuwen, P. W. N. M., Lutz, M. & Spek, A. L. (2000). Organometallics, 19, 872-883.]; Verheyen et al., 2019[Verheyen, T., Santillo, N., Marinelli, D., Petricci, E., De Borggraeve, W. M., Vaccaro, L. & Smet, M. (2019). ACS Appl. Polym. Mater. 1, 1496-1504.]), C—H bond aryl­ations (Li et al., 2016[Li, M., González-Esguevillas, M., Berritt, S., Yang, X., Bellomo, A. & Walsh, P. J. (2016). Angew. Chem. Int. Ed. 55, 2825-2829.]), and aryl chloride cross-couplings (Zhang et al., 2014[Zhang, J., Bellomo, A., Trongsiriwat, N., Jia, T., Carroll, P. J., Dreher, S. D., Tudge, M. T., Yin, H., Robinson, J. R., Schelter, E. J. & Walsh, P. J. (2014). J. Am. Chem. Soc. 136, 6276-6287.]). One of the most notable phenoxazine ligands is NiXantPhos (Fig. 1[link]). The key to their utility lies in the ability of the ligand to chelate a metal center using the central oxygen atom (O1 in the reported case) alongside the functional groups at the 4 and 6 positions. As best as we can tell, there is not yet a report of a phenoxazine ligand with hydroxyl functional groups at these same positions offering the same ability to chelate.

[Figure 1]
Figure 1
NiXantPhos ligand.

The reported compound consists of a 10-phenyl-10H-phenoxazine backbone with two hydroxyl moieties at the 4 and 6 positions of the phenoxazine ring, and this structure was obtained as a tetra­hydro­furan solvate (Fig. 2[link]). Similar to the other reported phenoxazine-based ligands, the phenoxazine fused ring system is not planar, with flexion at O1 and N1 resulting in an 18.92 (3)° deviation from planarity, as computed using mean planes that encompass each half of the three-ring structure (i.e., atoms C7–C12/N1/O1 and C13–C18/N1/O1). The plane of the N-phenyl group is nearly perpendicular to the phenoxazine ring structure, with a dihedral angle of 89.14 (6)° between the mean plane of the phenyl ring and the plane defined by N1,C10,C11.

[Figure 2]
Figure 2
Ellipsoid plot (50%) of the title solvate. The minor component of disorder for the THF solvent mol­ecule is omitted for the sake of clarity.

This compound was crystallized from a solution of toluene and tetra­hydro­furan, and the resulting structure solution shows a single tetra­hydro­furan molecule with its oxygen atom accepting two hydrogen-bonding inter­action from the phenoxazine hydroxyl groups. The inter­actions between O4 in the tetra­hydro­furan solvent with the O2 and O3 hydroxyl groups mimic a structure that a deprotonated, dianionic form of the title compound might adopt upon complexation with a metal ion. The inter­action between these mol­ecules could be classified according to the Jeffrey model as `moderate, mostly electrostatic' (Jeffrey, 1997[Jeffrey, G. A. (1997). An Introduction to Hydrogen Bonding. Oxford University Press.]) with donor–acceptor distances of 2.7729 (15) Å (O4⋯O2) and 2.7447 (15) Å (O4⋯O3) (Fig. 3[link], Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O4 0.93 (2) 1.88 (2) 2.7729 (15) 159.5 (19)
O3—H3⋯O4 0.91 (2) 1.88 (2) 2.7447 (15) 157.0 (19)
[Figure 3]
Figure 3
Solid-state structure of 10-phenyl-10H-phenoxazine-4,6-diol, with disordered tetra­hydro­furan solvate mol­ecule (50% ellipsoids). Hydrogen-bonding inter­actions between the two hydroxyl groups and the oxygen atom of tetra­hydro­furan are indicated by dashed lines.

One other important supra­molecular feature is a ππ stacking inter­action between inversion-related (1 − x, 1 − y, 1 − z) mol­ecules (Fig. 4[link]). One of the peripheral arene rings lies over the same ring in a neighboring mol­ecule. The centroid-to-centroid separation between these two rings is 3.6355 (11) Å.

[Figure 4]
Figure 4
Solid-state structure of 10-phenyl-10H-phenoxazine-4,6-diol with the major THF component (50% ellipsoids). An additional inversion-related (1 − x, 1 − y, 1 − z) mol­ecule is included, showing the ππ stacking distance of 3.6355 (11) Å.

Synthesis and crystallization

10-Phenyl-10H-phenoxazine was synthesized according to literature procedures (Liu et al., 2014[Liu, N., Wang, B., Chen, W., Liu, C., Wang, X. & Hu, Y. (2014). RSC Adv. 4, 51133-51139.]). With this compound in hand, an anhydrous deprotonation was performed on 39 mmol of starting material using 2.2 equivalents of n-butyl­lithium (2.5 M in hexa­nes) and N,N,N′,N′-tetra­methyl­ethane-1,2-di­amine in diethyl ether solvent at 273 K. The solution was allowed to warm to room temperature and then stirred overnight. The reaction mixture of the li­thia­ted 10-phenyl-10H-phenoxazine was then cooled again to 273 K and cannulated into a stirred solution of diethyl ether and four equivalents of trimethyl borate. The solution was allowed to warm to room temperature and then stirred overnight. This initial procedure was modeled after the one reported for the synthesis of NiXantPhos (van der Veen et al., 2009[Veen, L. A. van der, Keeven, P. H., Schoemaker, G. C., Reek, J. N. H., Kamer, P. C. J., van Leeuwen, P. W. N. M., Lutz, M. & Spek, A. L. (2000). Organometallics, 19, 872-883.]).

The lemon-yellow reaction mixture was evaporated on a rotary evaporator to dryness. The solids were redissolved in ∼500 ml of methanol and stirred until homogenous. A solution of methanol and six equivalents of urea hydrogen peroxide was prepared and then added dropwise at 273 K to the reaction mixture. The reaction darkened considerably, to a deep red. After stirring overnight, the reaction mixture was concentrated to one quarter of its initial volume using a rotary evaporator before being diluted with ∼400 ml of distilled water. The solution pH was adjusted using hydro­chloric acid until it was neutral to slightly acidic (pH 4–6 indicated by pH paper). At this point the reaction mixture contained a considerable amount of solid that was identified as the 10-phenyl-10H-phenoxazine-4,6-diol, so the reaction mixture was filtered to obtain this crude brown–red solid. The subsequent procedure is modeled after the hy­droxy­lation described by Gupta et al. (2016[Gupta, S., Chaudhary, P., Srivastava, V. & Kandasamy, J. (2016). Tetrahedron Lett. 57, 2506-2510.]).

The compound was then purified using silica gel column chromatography with a solvent mixture of 15% ethyl acetate in hexa­nes as an eluent. The eluent polarity was increased by increasing the concentration of ethyl acetate up to 35% over the course of the procedure. The final compound was obtained in 50% yield.

Single crystals suitable for X-ray analysis were obtained using a vapor diffusion method. A small portion of the title compound was dissolved in tetra­hydro­furan and transferred to a small cylindrical vial that fitted fully into a standard 20 ml scintillation vial. The volume around the small vial was then filled with toluene until it reached approximately half the capacity of the remaining volume. The 20 ml vial was capped with the inter­nal vial uncapped to allow for vapors diffusion. In this embodiment, the tetra­hydro­furan solvent will evaporate and dissolve into the toluene solution, concentrating the title compound in the tetra­hydro­furan vial.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The positions of the two hydroxyl H atoms involved in hydrogen bonding, H2 and H3, were refined from difference-map peaks as proof of their correct assignment. The tetra­hydro­furan mol­ecule was found to be disordered, and all atoms except for oxygen were modeled across two positions. Due to the positioning of the disordered parts, SHELXL commands EADP and SAME were used to ensure a stable refinement. Disordered part occupancies refined to 0.511 (8) and 0.489 (8).

Table 2
Experimental details

Crystal data
Chemical formula C18H13NO3·C4H8O
Mr 363.40
Crystal system, space group Monoclinic, P21/n
Temperature (K) 100
a, b, c (Å) 8.2694 (3), 21.1783 (8), 10.7050 (4)
β (°) 111.117 (1)
V3) 1748.89 (11)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.10
Crystal size (mm) 0.37 × 0.29 × 0.14
 
Data collection
Diffractometer Bruker D8 Quest CMOS Photon 100
Absorption correction Multi-scan (SADABS; Bruker, 2018[Bruker (2018). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.692, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections 27791, 3212, 2674
Rint 0.046
(sin θ/λ)max−1) 0.604
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.090, 1.06
No. of reflections 3212
No. of parameters 271
No. of restraints 76
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.17, −0.25
Computer programs: SAINT (Bruker, 2018[Bruker (2018). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and 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.]).

Structural data


Computing details top

Data collection: SAINT (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); 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).

10-Phenyl-10H-phenoxazine-4,6-diol tetrahydrofuran monosolvate top
Crystal data top
C18H13NO3·C4H8OF(000) = 768
Mr = 363.40Dx = 1.380 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.2694 (3) ÅCell parameters from 9962 reflections
b = 21.1783 (8) Åθ = 3.3–25.4°
c = 10.7050 (4) ŵ = 0.10 mm1
β = 111.117 (1)°T = 100 K
V = 1748.89 (11) Å3Plank, colourless
Z = 40.37 × 0.29 × 0.14 mm
Data collection top
Bruker D8 Quest CMOS Photon 100
diffractometer
2674 reflections with I > 2σ(I)
ω and φ scansRint = 0.046
Absorption correction: multi-scan
(SADABS; Bruker, 2018)
θmax = 25.4°, θmin = 3.3°
Tmin = 0.692, Tmax = 0.745h = 99
27791 measured reflectionsk = 2525
3212 independent reflectionsl = 1211
Refinement top
Refinement on F276 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0442P)2 + 0.5498P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3212 reflectionsΔρmax = 0.17 e Å3
271 parametersΔρmin = 0.25 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.48901 (12)0.35256 (4)0.42474 (9)0.0174 (2)
O20.75882 (13)0.27069 (5)0.47249 (11)0.0234 (2)
H20.711 (3)0.2971 (11)0.399 (2)0.057 (6)*
O30.46637 (13)0.44236 (5)0.23825 (10)0.0211 (2)
H30.532 (3)0.4065 (11)0.259 (2)0.056 (6)*
N10.32048 (14)0.36710 (5)0.60817 (11)0.0170 (3)
C10.33959 (19)0.42379 (7)0.81239 (15)0.0222 (3)
H10.4375720.4460680.8088790.027*
C20.2799 (2)0.43476 (7)0.91599 (15)0.0262 (4)
H2A0.3377150.4643650.9841250.031*
C30.1361 (2)0.40269 (7)0.92040 (16)0.0271 (4)
H3A0.0957700.4101820.9916890.033*
C40.0514 (2)0.35982 (7)0.82124 (16)0.0254 (3)
H40.0476900.3380860.8241470.030*
C50.11060 (18)0.34832 (7)0.71710 (15)0.0205 (3)
H50.0521810.3189180.6486930.025*
C60.25548 (18)0.38013 (6)0.71400 (14)0.0166 (3)
C70.73513 (18)0.23963 (7)0.67830 (15)0.0216 (3)
H70.8267370.2102080.6924600.026*
C80.65703 (18)0.24613 (7)0.77205 (15)0.0206 (3)
H80.6973780.2213940.8513630.025*
C90.52065 (17)0.28807 (6)0.75289 (14)0.0173 (3)
H90.4679940.2916740.8181440.021*
C100.46193 (17)0.32481 (6)0.63683 (13)0.0154 (3)
C110.54326 (17)0.31868 (6)0.54403 (13)0.0155 (3)
C120.67853 (17)0.27654 (6)0.56296 (14)0.0178 (3)
C130.39217 (16)0.40665 (6)0.42331 (13)0.0148 (3)
C140.30677 (17)0.41490 (6)0.51257 (13)0.0155 (3)
C150.20860 (17)0.46948 (6)0.50202 (14)0.0175 (3)
H150.1492040.4764070.5620100.021*
C160.19783 (17)0.51370 (7)0.40367 (14)0.0193 (3)
H160.1301450.5506740.3968670.023*
C170.28348 (17)0.50509 (7)0.31540 (14)0.0190 (3)
H170.2745210.5357520.2484570.023*
C180.38298 (17)0.45100 (7)0.32567 (13)0.0162 (3)
O40.69658 (12)0.34718 (5)0.24978 (10)0.0227 (2)
C190.8657 (14)0.3770 (8)0.3042 (10)0.0246 (11)0.511 (8)
H19A0.9573770.3457690.3489150.030*0.511 (8)
H19B0.8673450.4107020.3686990.030*0.511 (8)
C200.8879 (13)0.4040 (5)0.1804 (8)0.0263 (13)0.511 (8)
H20A1.0121570.4086020.1936790.032*0.511 (8)
H20B0.8308230.4457290.1573280.032*0.511 (8)
C210.8004 (6)0.3555 (2)0.0715 (4)0.0213 (10)0.511 (8)
H21A0.7492120.3761220.0170700.026*0.511 (8)
H21B0.8843540.3230960.0670030.026*0.511 (8)
C220.660 (2)0.3262 (7)0.1139 (8)0.0221 (4)0.511 (8)
H22A0.5436250.3407200.0547520.026*0.511 (8)
H22B0.6638260.2795740.1098590.026*0.511 (8)
C19'0.8568 (15)0.3837 (9)0.2936 (10)0.0246 (11)0.489 (8)
H19C0.9492840.3598630.3628410.030*0.489 (8)
H19D0.8390360.4240970.3332750.030*0.489 (8)
C20'0.9104 (13)0.3965 (6)0.1747 (9)0.0263 (13)0.489 (8)
H20C1.0059490.3682060.1751620.032*0.489 (8)
H20D0.9469600.4409130.1737060.032*0.489 (8)
C21'0.7445 (7)0.3824 (3)0.0560 (4)0.0240 (11)0.489 (8)
H21C0.7699270.3685160.0232440.029*0.489 (8)
H21D0.6667590.4195990.0318800.029*0.489 (8)
C22'0.667 (2)0.3288 (7)0.1124 (8)0.0221 (4)0.489 (8)
H22C0.5409680.3243900.0605920.026*0.489 (8)
H22D0.7245850.2882280.1096580.026*0.489 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0208 (5)0.0185 (5)0.0146 (5)0.0032 (4)0.0084 (4)0.0009 (4)
O20.0243 (5)0.0252 (6)0.0250 (6)0.0046 (4)0.0141 (5)0.0002 (5)
O30.0245 (5)0.0250 (6)0.0181 (5)0.0001 (4)0.0127 (4)0.0015 (4)
N10.0187 (6)0.0189 (6)0.0159 (6)0.0034 (5)0.0092 (5)0.0036 (5)
C10.0257 (8)0.0220 (7)0.0207 (8)0.0019 (6)0.0105 (6)0.0024 (6)
C20.0413 (9)0.0209 (8)0.0187 (8)0.0016 (7)0.0134 (7)0.0003 (6)
C30.0411 (9)0.0258 (8)0.0239 (8)0.0083 (7)0.0231 (7)0.0065 (7)
C40.0267 (8)0.0256 (8)0.0312 (9)0.0026 (6)0.0194 (7)0.0071 (7)
C50.0225 (7)0.0181 (7)0.0226 (8)0.0024 (6)0.0103 (6)0.0017 (6)
C60.0206 (7)0.0158 (7)0.0157 (7)0.0046 (5)0.0093 (6)0.0041 (6)
C70.0184 (7)0.0189 (7)0.0269 (8)0.0027 (6)0.0075 (6)0.0013 (6)
C80.0207 (7)0.0184 (7)0.0204 (7)0.0010 (6)0.0047 (6)0.0033 (6)
C90.0184 (7)0.0180 (7)0.0156 (7)0.0027 (5)0.0064 (6)0.0009 (5)
C100.0148 (6)0.0133 (6)0.0166 (7)0.0024 (5)0.0039 (5)0.0030 (5)
C110.0168 (7)0.0150 (7)0.0128 (7)0.0029 (5)0.0030 (5)0.0004 (5)
C120.0168 (7)0.0175 (7)0.0204 (7)0.0036 (5)0.0083 (6)0.0044 (6)
C130.0114 (6)0.0155 (7)0.0157 (7)0.0005 (5)0.0025 (5)0.0018 (5)
C140.0135 (6)0.0183 (7)0.0135 (7)0.0032 (5)0.0035 (5)0.0001 (5)
C150.0150 (7)0.0217 (7)0.0167 (7)0.0000 (5)0.0069 (6)0.0005 (6)
C160.0165 (7)0.0194 (7)0.0214 (7)0.0023 (5)0.0061 (6)0.0021 (6)
C170.0177 (7)0.0204 (7)0.0170 (7)0.0012 (6)0.0040 (6)0.0043 (6)
C180.0128 (6)0.0223 (7)0.0135 (7)0.0053 (5)0.0049 (5)0.0032 (6)
O40.0216 (5)0.0306 (6)0.0188 (5)0.0030 (4)0.0108 (4)0.0032 (4)
C190.0197 (11)0.032 (3)0.0227 (14)0.0022 (15)0.0077 (10)0.0079 (15)
C200.026 (2)0.024 (2)0.0312 (10)0.0029 (17)0.0131 (11)0.0000 (10)
C210.022 (2)0.024 (2)0.0198 (16)0.0008 (15)0.0102 (15)0.0017 (16)
C220.0231 (11)0.0262 (11)0.0187 (7)0.0033 (7)0.0098 (6)0.0042 (7)
C19'0.0197 (11)0.032 (3)0.0227 (14)0.0022 (15)0.0077 (10)0.0079 (15)
C20'0.026 (2)0.024 (2)0.0312 (10)0.0029 (17)0.0131 (11)0.0000 (10)
C21'0.025 (2)0.028 (2)0.0222 (18)0.0051 (17)0.0132 (16)0.0011 (17)
C22'0.0231 (11)0.0262 (11)0.0187 (7)0.0033 (7)0.0098 (6)0.0042 (7)
Geometric parameters (Å, º) top
O1—C111.3908 (16)C15—H150.9500
O1—C131.3946 (16)C15—C161.388 (2)
O2—H20.93 (2)C16—H160.9500
O2—C121.3628 (17)C16—C171.382 (2)
O3—H30.91 (2)C17—H170.9500
O3—C181.3601 (16)C17—C181.391 (2)
N1—C61.4448 (17)O4—C191.451 (5)
N1—C101.4162 (17)O4—C221.445 (5)
N1—C141.4147 (17)O4—C19'1.457 (5)
C1—H10.9500O4—C22'1.453 (5)
C1—C21.387 (2)C19—H19A0.9900
C1—C61.386 (2)C19—H19B0.9900
C2—H2A0.9500C19—C201.514 (6)
C2—C31.385 (2)C20—H20A0.9900
C3—H3A0.9500C20—H20B0.9900
C3—C41.381 (2)C20—C211.526 (7)
C4—H40.9500C21—H21A0.9900
C4—C51.391 (2)C21—H21B0.9900
C5—H50.9500C21—C221.523 (7)
C5—C61.385 (2)C22—H22A0.9900
C7—H70.9500C22—H22B0.9900
C7—C81.382 (2)C19'—H19C0.9900
C7—C121.392 (2)C19'—H19D0.9900
C8—H80.9500C19'—C20'1.515 (6)
C8—C91.3916 (19)C20'—H20C0.9900
C9—H90.9500C20'—H20D0.9900
C9—C101.3965 (19)C20'—C21'1.526 (7)
C10—C111.3920 (19)C21'—H21C0.9900
C11—C121.3876 (19)C21'—H21D0.9900
C13—C141.3887 (19)C21'—C22'1.532 (8)
C13—C181.3868 (19)C22'—H22C0.9900
C14—C151.3936 (19)C22'—H22D0.9900
C11—O1—C13115.33 (10)C16—C17—C18119.26 (13)
C12—O2—H2112.7 (13)C18—C17—H17120.4
C18—O3—H3110.4 (13)O3—C18—C13121.59 (13)
C10—N1—C6117.55 (11)O3—C18—C17119.23 (12)
C14—N1—C6118.36 (11)C13—C18—C17119.17 (13)
C14—N1—C10117.00 (11)C22—O4—C19111.1 (6)
C2—C1—H1120.2C22'—O4—C19'105.8 (6)
C6—C1—H1120.2O4—C19—H19A111.3
C6—C1—C2119.60 (14)O4—C19—H19B111.3
C1—C2—H2A119.9O4—C19—C20102.5 (6)
C3—C2—C1120.17 (14)H19A—C19—H19B109.2
C3—C2—H2A119.9C20—C19—H19A111.3
C2—C3—H3A120.0C20—C19—H19B111.3
C4—C3—C2120.04 (14)C19—C20—H20A111.0
C4—C3—H3A120.0C19—C20—H20B111.0
C3—C4—H4119.9C19—C20—C21103.9 (8)
C3—C4—C5120.24 (14)H20A—C20—H20B109.0
C5—C4—H4119.9C21—C20—H20A111.0
C4—C5—H5120.3C21—C20—H20B111.0
C6—C5—C4119.42 (14)C20—C21—H21A110.9
C6—C5—H5120.3C20—C21—H21B110.9
C1—C6—N1119.79 (12)H21A—C21—H21B108.9
C5—C6—N1119.68 (12)C22—C21—C20104.5 (5)
C5—C6—C1120.52 (13)C22—C21—H21A110.9
C8—C7—H7120.2C22—C21—H21B110.9
C8—C7—C12119.50 (13)O4—C22—C21105.6 (4)
C12—C7—H7120.2O4—C22—H22A110.6
C7—C8—H8119.3O4—C22—H22B110.6
C7—C8—C9121.50 (13)C21—C22—H22A110.6
C9—C8—H8119.3C21—C22—H22B110.6
C8—C9—H9120.3H22A—C22—H22B108.8
C8—C9—C10119.36 (13)O4—C19'—H19C109.8
C10—C9—H9120.3O4—C19'—H19D109.8
C9—C10—N1122.71 (12)O4—C19'—C20'109.4 (7)
C11—C10—N1118.56 (12)H19C—C19'—H19D108.2
C11—C10—C9118.71 (12)C20'—C19'—H19C109.8
O1—C11—C10121.88 (12)C20'—C19'—H19D109.8
C12—C11—O1116.25 (12)C19'—C20'—H20C111.3
C12—C11—C10121.82 (12)C19'—C20'—H20D111.3
O2—C12—C7119.02 (12)C19'—C20'—C21'102.5 (7)
O2—C12—C11121.89 (13)H20C—C20'—H20D109.2
C11—C12—C7119.09 (13)C21'—C20'—H20C111.3
C14—C13—O1121.88 (12)C21'—C20'—H20D111.3
C18—C13—O1116.09 (12)C20'—C21'—H21C111.5
C18—C13—C14122.01 (12)C20'—C21'—H21D111.5
C13—C14—N1118.66 (12)C20'—C21'—C22'101.3 (7)
C13—C14—C15118.31 (12)H21C—C21'—H21D109.3
C15—C14—N1123.01 (12)C22'—C21'—H21C111.5
C14—C15—H15120.1C22'—C21'—H21D111.5
C16—C15—C14119.84 (13)O4—C22'—C21'104.9 (5)
C16—C15—H15120.1O4—C22'—H22C110.8
C15—C16—H16119.3O4—C22'—H22D110.8
C17—C16—C15121.41 (13)C21'—C22'—H22C110.8
C17—C16—H16119.3C21'—C22'—H22D110.8
C16—C17—H17120.4H22C—C22'—H22D108.8
O1—C11—C12—O22.79 (18)C10—N1—C14—C15160.96 (12)
O1—C11—C12—C7177.89 (12)C10—C11—C12—O2179.69 (12)
O1—C13—C14—N10.62 (18)C10—C11—C12—C70.4 (2)
O1—C13—C14—C15178.17 (12)C11—O1—C13—C1420.88 (17)
O1—C13—C18—O31.08 (18)C11—O1—C13—C18160.53 (11)
O1—C13—C18—C17177.75 (11)C12—C7—C8—C91.1 (2)
N1—C10—C11—O10.26 (19)C13—O1—C11—C1020.67 (17)
N1—C10—C11—C12177.64 (12)C13—O1—C11—C12161.81 (11)
N1—C14—C15—C16178.48 (12)C13—C14—C15—C160.25 (19)
C1—C2—C3—C40.2 (2)C14—N1—C6—C168.80 (17)
C2—C1—C6—N1178.07 (12)C14—N1—C6—C5111.92 (14)
C2—C1—C6—C51.2 (2)C14—N1—C10—C9160.93 (12)
C2—C3—C4—C50.4 (2)C14—N1—C10—C1120.49 (17)
C3—C4—C5—C60.2 (2)C14—C13—C18—O3179.66 (12)
C4—C5—C6—N1178.27 (12)C14—C13—C18—C170.84 (19)
C4—C5—C6—C11.0 (2)C14—C15—C16—C170.3 (2)
C6—N1—C10—C910.81 (18)C15—C16—C17—C180.2 (2)
C6—N1—C10—C11170.60 (12)C16—C17—C18—O3179.60 (12)
C6—N1—C14—C13170.18 (12)C16—C17—C18—C130.7 (2)
C6—N1—C14—C1511.10 (19)C18—C13—C14—N1179.12 (12)
C6—C1—C2—C30.6 (2)C18—C13—C14—C150.34 (19)
C7—C8—C9—C100.5 (2)O4—C19—C20—C2135.2 (14)
C8—C7—C12—O2178.66 (12)O4—C19'—C20'—C21'16.4 (16)
C8—C7—C12—C110.7 (2)C19—O4—C22—C2110.8 (16)
C8—C9—C10—N1178.00 (12)C19—C20—C21—C2229.2 (14)
C8—C9—C10—C110.58 (19)C20—C21—C22—O412.0 (14)
C9—C10—C11—O1178.38 (11)C22—O4—C19—C2029.1 (15)
C9—C10—C11—C121.0 (2)C19'—O4—C22'—C21'30.9 (15)
C10—N1—C6—C180.90 (16)C19'—C20'—C21'—C22'33.6 (14)
C10—N1—C6—C598.38 (15)C20'—C21'—C22'—O440.6 (14)
C10—N1—C14—C1320.31 (18)C22'—O4—C19'—C20'8.9 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O40.93 (2)1.88 (2)2.7729 (15)159.5 (19)
O3—H3···O40.91 (2)1.88 (2)2.7447 (15)157.0 (19)
 

Acknowledgements

The authors would like to thank the University of Pennsylvania for data-collection services and both Professor Louise Dawe (Wilfrid Laurier University) and Dr Amy Sarjeant (Bristol Myers Squibb) for their patient teaching on our journey into crystallography.

Funding information

Funding for this research was provided by: program manager Dr Imre Gyuk through the US Department of Energy, Office of Electricity, and Davidson College Faculty Study and Research (grant to ACW, CHB, DT). Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell Inter­national, Inc., for the US Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. The views expressed in this article do not necessarily represent the views of the US Department of Energy or the United States Government.

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