Crystal structure of a bis-4-aza­tetra­cyclo[5.3.2.02,6.08,10]dodec-11-ene-3,5-dione compound

Jiang, C.Y.; Staples, R.J.; Biros, S.M.

doi:10.1107/S2056989025003500

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ISSN: 2056-9890

Volume 81| Part 5| May 2025| Pages 425-428

https://doi.org/10.1107/S2056989025003500

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Crystal structure of a bis-4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-ene-3,5-dione compound

Christina Yu Jiang,^a Richard J. Staples ^b and Shannon M. Biros ^a ^*

^aDepartment of Chemistry, Grand Valley State University, Allendale, MI 49401, USA, and ^bCenter for Crystallographic Research, Department of Chemistry and Chemical Biology, Michigan State University, East Lansing, MI 48824, USA
^*Correspondence e-mail: [email protected]

Edited by N. Alvarez Failache, Universidad de la Repüblica, Uruguay (Received 14 April 2025; accepted 17 April 2025; online 24 April 2025)

In the molecule of 4-({3-[(3,5-dioxo-4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-en-4-yl)methyl]phenyl}methyl)-4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-ene-3,5-dione, C₃₀H₂₈N₂O₄, which contains two substituted [2.2.2]bicyclooctene ring systems linked through a m-xylenediamine ring, the six-membered rings of the bicyclooctene ring systems adopt nearly perfect boat conformations as determined from Cremer–Pople analysis. Both ring systems are fused to a five-membered imide ring that is oriented endo to a bridgehead cyclopropyl ring. The crystal structure features C=O⋯π interactions along with C—H⋯O hydrogen bonds.

Keywords: crystal structure; C-H⋯O hydrogen bonds; C=O⋯π interaction; imide; [2.2.2]cyclooctene.

CCDC reference: 2444823

1. Chemical context

The upper-level synthetic organic laboratory course at Grand Valley State University (GVSU) has exploited the chemistry of compound a for its ease of preparation (Kohler et al., 1939 ; Kurtz & Johnson, 1989 ), readily interpretable ¹H, ¹³C, COSY and HSQC NMR spectra, and its reactivity with primary amines (Fig. 1). The resulting imide products happen to be quite crystalline and we have reported the structures of three of these compounds in this journal (Hulsman et al., 2020 ; Bajko et al., 2024 ). Anhydride a has been used as a scaffold for the preparation of many new compounds, with one in particular earning approval as a treatment for smallpox (Tecovirimat; Bailey et al., 2007 ; Hughes 2019 ). We report here the crystal structure of a bis-imide derived from anhydride a where the [2.2.2]cyclooctene ring systems have been linked through a meta-xylenediamine core.

Figure 1
Reaction of anhydride (a) and m-xylenediamine to give compound I.

2. Structural commentary

The structure of compound I is shown in Fig. 2 along with the atom-numbering scheme. The meta-methylene-substituted benzene ring (C13-C18) displays two structurally identical, yet crystallographically unique, 4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-ene-3,5-dione ring systems. The bicyclo[2.2.2]cyclooctene ring systems within each tetracycle feature C=C bonds with distances of 1.333 (2) and 1.330 (2) Å for C6—C7 and C6A—C7A, respectively. The cyclohexene rings (C3—C8 and C3A—C8A) both adopt a nearly perfect boat conformation with Cremer–Pople puckering parameters of 89.89 (10) and 90.82 (11)° for φ and 299.84 (10) and 298.70 (11)° for θ (where φ = 90° and θ = 0° is an ideal boat; Cremer & Pople, 1975 ). The imide rings (N1/C1/C3/C4/C2 and N1A/C1A/C3A/C4A/C2A) are oriented endo relative to the bridgehead carbons C9/C10 and C9A/C10A. The tetracyclic ring systems are oriented in nearly opposite directions relative to the planar benzene ring with a N1—C12—C19—N1A torsion angle of 135.89 (10)°.

Figure 2
The molecular structure of compound I along with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level using standard CPK colors.

3. Supramolecular features

Dimers of compound I are held together through one C=O⋯π interaction (Mooibroek et al., 2008 ; Li et al., 2019 ) and two C—H⋯O hydrogen bonds (Fig. 3; Sutor, 1962 , 1963 ; Steiner, 1996 ). The C=O⋯π interaction C1=O1 and the centroid (Cg) of the imide N1A/C1A/C3A/C4A/C2A ring (symmetry code: −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z) has an O⋯Cg distance of 2.9964 (12) Å with a C=O⋯Cg angle of 141.18 (9)°. The C—H⋯O hydrogen bonds are present between C3A(H3A), C9A(H9A) and O2A (symmetry code: −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z, Table 1). Each carbonyl oxygen of the N1A/C1A/C3A/C4A/C2A imide ring hosts an additional C—H⋯O hydrogen bond that links the dimers into sheets that lie in the ab plane (Figs. 4 and 5). These interactions are between atoms C9(H9) and O1A (symmetry code: x, y − 1, z) and C7A(H7A) and O2A (symmetry code: −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3A—H3A⋯O2Aⁱ	1.00	2.53	3.3958 (17)	144
C9A—H9A⋯O2Aⁱ	1.00	2.51	3.3041 (17)	136
C9—H9⋯O1Aⁱⁱ	1.00	2.41	3.1985 (17)	135
C7A—H7A⋯O2Aⁱⁱⁱ	0.95	2.52	3.1135 (18)	121
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Depiction of the C=O⋯π interaction (orange, dotted line) and C—H⋯O hydrogen bonds (green, dashed lines) that form dimers of compound I in the solid state. This figure was drawn using a ball-and-stick model with standard CPK colors; only hydrogen atoms that are involved in a hydrogen bond are shown for clarity. Symmetry code: (i) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z.

Figure 4
The two additional intermolecular C—H⋯O hydrogen bonds (green, dashed lines) that are present in the crystal of compound I using a standard CPK colors and a ball-and-stick model. Only those hydrogen atoms are shown that are involved in a depicted hydrogen bond. Symmetry codes: (ii) x, y − 1, z; (iii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

Figure 5
A packing diagram of the crystal of compound I viewed down the b-axis showing the supramolecular sheets formed via intermolecular C=O⋯π interactions (orange, dotted lines) and C—H⋯O hydrogen bonds (green, dashed lines). Drawn using a ball-and-stick model with standard CPK colors, only hydrogen atoms involved in an interaction are shown for clarity. The outline of one unit cell is drawn with a pink, dashed line.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.45, updates through June 2024; Groom et al., 2016 ) for structures containing a tricyclo[2.2.2.1^4,5]cyclononene ring system resulted in 31 hits. We highlight here three compounds that we found structurally interesting. Structure BOTZIW features four of these tricycles appended to the pyrrole rings of a porphyrin–Pt^II complex (Okujima et al., 2019 ). In TPCDDD, the tricyclic ring system of the title compound is incorporated into a stunning trichloropentacyclodiene structure (Mock et al., 1972 ). Lastly, Kaftory (1978 ) crystallized a diadduct formed from two derivatives of the parent tricyclic ring system.

5. Synthesis and crystallization

The anhydride shown in Fig. 1 (205 mg, 1.08 mmol, Kohler et al., 1939, Kurtz & Johnson, 1989) was dissolved in 2.0 mL of xylenes in a vial at ambient temperature, then added to a round-bottom flask equipped with a magnetic stir bar. In a separate vial at ambient temperature, 0.1 mL (0.76 mmol) of m-xylenediamine were dissolved in 1.0 mL of xylenes and then transferred dropwise to the round-bottom flask. A precipitate formed immediately. The reaction mixture was heated to reflux using an oil bath for 30 minutes, allowed to cool to room temperature and diluted with 20 mL of hexanes. After standing overnight, the solid was isolated using a Hirsch funnel and recrystallized from hot water. After a few days, orange–yellowish needles appeared in the flask and were isolated. A percentage yield was not determined for this reaction as the amount of product obtained was quite small. Crystals suitable for X-ray diffraction were grown by layering a roughly equal volume of water on top of a dilute sample of the product in DMSO-d₆ in an NMR tube and allowing the solution to sit for two weeks. LR-MS (ESI) m/z: [M + H]⁺ calculated for [C₃₀H₂₈N₂O₄H]⁺ 480.2; found, 480.8.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms bonded to carbon atoms were placed in calculated positions and refined as riding: U_iso(H) = 1.2U_eq(C) for methylene, methine, aromatic and alkene groups.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₀H₂₈N₂O₄
M_r	480.54
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.26039 (13), 12.26667 (15), 33.0963 (3)
V (Å³)	4571.51 (9)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.75
Crystal size (mm)	0.22 × 0.10 × 0.04

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.824, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	32235, 4946, 4324
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.07
No. of reflections	4946
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21
Computer programs: CrysAlis PRO (Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), CrystalMaker (Palmer, 2007 ) and OLEX2 (Dolomanov et al., 2009 ; Bourhis et al., 2015 ).

Supporting information

CCDC reference: 2444823

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003500/ny2012sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003500/ny2012Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003500/ny2012Isup3.cml

checkCIF report

Computing details top

4-({3-[(3,5-Dioxo-4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-en-4-yl)methyl]phenyl}methyl)-4-azatetracyclo[5.3.2.0^2,6.0^8,10]dodec-11-ene-3,5-dione top

Crystal data top

C₃₀H₂₈N₂O₄	D_x = 1.396 Mg m⁻³
M_r = 480.54	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 15558 reflections
a = 11.26039 (13) Å	θ = 2.7–79.2°
b = 12.26667 (15) Å	µ = 0.75 mm⁻¹
c = 33.0963 (3) Å	T = 100 K
V = 4571.51 (9) Å³	Needle, colourless
Z = 8	0.22 × 0.10 × 0.04 mm
F(000) = 2032

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	4946 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	4324 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.045
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.0°, θ_min = 2.7°
ω scans	h = −14→14
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2024)	k = −15→15
T_min = 0.824, T_max = 1.000	l = −27→42
32235 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.056P)² + 1.9036P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
4946 reflections	Δρ_max = 0.30 e Å⁻³
325 parameters	Δρ_min = −0.21 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O1	0.65542 (9)	0.22161 (9)	0.35506 (3)	0.0280 (2)
O2	0.64114 (9)	0.24129 (8)	0.49249 (3)	0.0270 (2)
N1	0.66306 (10)	0.25121 (9)	0.42358 (3)	0.0214 (2)
C1	0.62872 (12)	0.19453 (11)	0.38916 (4)	0.0214 (3)
C2	0.62238 (12)	0.20430 (11)	0.45908 (4)	0.0213 (3)
C3	0.55555 (12)	0.09689 (11)	0.40195 (4)	0.0209 (3)
H3	0.595702	0.028144	0.393166	0.025*
C4	0.55262 (12)	0.10284 (10)	0.44859 (4)	0.0203 (3)
H4	0.592615	0.037261	0.460293	0.024*
C5	0.42197 (12)	0.10868 (11)	0.46364 (4)	0.0219 (3)
H5	0.417830	0.115687	0.493710	0.026*
C6	0.36415 (12)	0.20413 (11)	0.44290 (4)	0.0239 (3)
H6	0.328886	0.262805	0.457289	0.029*
C7	0.36653 (12)	0.19948 (11)	0.40267 (4)	0.0248 (3)
H7	0.333527	0.254937	0.386074	0.030*
C8	0.42562 (12)	0.09943 (11)	0.38556 (4)	0.0228 (3)
H8	0.423454	0.098893	0.355357	0.027*
C9	0.36814 (12)	−0.00344 (11)	0.40349 (4)	0.0243 (3)
H9	0.390834	−0.074758	0.391057	0.029*
C10	0.36600 (12)	0.00170 (11)	0.44909 (4)	0.0236 (3)
H10	0.387699	−0.066222	0.464081	0.028*
C11	0.25107 (13)	0.00056 (12)	0.42566 (4)	0.0274 (3)
H11A	0.204812	0.069108	0.424354	0.033*
H11B	0.202722	−0.066814	0.426447	0.033*
C12	0.73641 (12)	0.34996 (11)	0.42292 (4)	0.0240 (3)
H12A	0.785149	0.350056	0.398026	0.029*
H12B	0.791177	0.348634	0.446316	0.029*
C13	0.66361 (12)	0.45373 (11)	0.42439 (4)	0.0223 (3)
C14	0.61529 (12)	0.49699 (11)	0.38902 (4)	0.0226 (3)
H14	0.628213	0.460844	0.364018	0.027*
C15	0.54809 (12)	0.59283 (11)	0.38990 (4)	0.0227 (3)
C16	0.53009 (13)	0.64554 (12)	0.42667 (4)	0.0263 (3)
H16	0.485926	0.711479	0.427569	0.032*
C17	0.57654 (14)	0.60192 (12)	0.46204 (4)	0.0294 (3)
H17	0.562699	0.637477	0.487103	0.035*
C18	0.64301 (13)	0.50677 (12)	0.46097 (4)	0.0263 (3)
H18	0.674638	0.477605	0.485287	0.032*
C19	0.49046 (12)	0.63590 (11)	0.35169 (4)	0.0243 (3)
H19A	0.451709	0.574514	0.337436	0.029*
H19B	0.427710	0.688583	0.359291	0.029*
O1A	0.54311 (10)	0.86502 (8)	0.34502 (3)	0.0302 (2)
O2A	0.63097 (10)	0.53584 (8)	0.28983 (3)	0.0315 (2)
N1A	0.57312 (10)	0.68934 (9)	0.32389 (3)	0.0214 (2)
C1A	0.58996 (12)	0.80106 (11)	0.32221 (4)	0.0219 (3)
C2A	0.63556 (12)	0.63386 (11)	0.29434 (4)	0.0229 (3)
C3A	0.67160 (12)	0.82669 (11)	0.28732 (4)	0.0214 (3)
H3A	0.744287	0.865214	0.297186	0.026*
C4A	0.70497 (12)	0.71488 (11)	0.26934 (4)	0.0215 (3)
H4A	0.792121	0.701612	0.272446	0.026*
C5A	0.66956 (13)	0.71028 (11)	0.22382 (4)	0.0238 (3)
H5A	0.689249	0.638089	0.211481	0.029*
C6A	0.53899 (13)	0.73366 (12)	0.22192 (4)	0.0258 (3)
H6A	0.483456	0.684407	0.210359	0.031*
C7A	0.50724 (13)	0.82896 (12)	0.23773 (4)	0.0260 (3)
H7A	0.427000	0.852806	0.238485	0.031*
C8A	0.60774 (13)	0.89626 (11)	0.25435 (4)	0.0239 (3)
H8A	0.579303	0.967581	0.265335	0.029*
C9A	0.70274 (13)	0.91170 (12)	0.22165 (4)	0.0265 (3)
H9A	0.767960	0.964581	0.227680	0.032*
C10A	0.73880 (13)	0.80335 (12)	0.20376 (4)	0.0262 (3)
H10A	0.825524	0.791281	0.199034	0.031*
C11A	0.67816 (15)	0.88829 (12)	0.17785 (4)	0.0301 (3)
H11C	0.726822	0.926744	0.157413	0.036*
H11D	0.594763	0.874818	0.169802	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0300 (5)	0.0369 (6)	0.0171 (4)	−0.0039 (4)	0.0019 (4)	0.0026 (4)
O2	0.0357 (5)	0.0285 (5)	0.0168 (4)	−0.0029 (4)	−0.0039 (4)	−0.0007 (4)
N1	0.0236 (5)	0.0237 (5)	0.0169 (5)	−0.0009 (4)	−0.0013 (4)	0.0019 (4)
C1	0.0208 (6)	0.0259 (6)	0.0174 (6)	0.0022 (5)	−0.0004 (5)	0.0004 (5)
C2	0.0234 (6)	0.0227 (6)	0.0178 (6)	0.0024 (5)	−0.0014 (5)	0.0023 (5)
C3	0.0242 (6)	0.0227 (6)	0.0159 (6)	0.0011 (5)	0.0009 (5)	−0.0004 (4)
C4	0.0252 (6)	0.0207 (6)	0.0151 (5)	0.0014 (5)	−0.0009 (5)	0.0017 (4)
C5	0.0271 (6)	0.0224 (6)	0.0161 (5)	0.0002 (5)	0.0024 (5)	0.0006 (5)
C6	0.0245 (6)	0.0217 (6)	0.0256 (7)	0.0019 (5)	0.0029 (5)	−0.0011 (5)
C7	0.0240 (6)	0.0249 (6)	0.0255 (6)	0.0018 (5)	−0.0015 (5)	0.0059 (5)
C8	0.0258 (6)	0.0278 (7)	0.0149 (5)	−0.0008 (5)	−0.0005 (5)	0.0005 (5)
C9	0.0270 (7)	0.0252 (6)	0.0208 (6)	−0.0026 (5)	−0.0003 (5)	−0.0028 (5)
C10	0.0268 (7)	0.0241 (6)	0.0197 (6)	−0.0016 (5)	0.0011 (5)	0.0024 (5)
C11	0.0265 (7)	0.0298 (7)	0.0257 (6)	−0.0043 (5)	0.0007 (5)	0.0008 (5)
C12	0.0240 (6)	0.0249 (7)	0.0230 (6)	−0.0027 (5)	−0.0015 (5)	0.0025 (5)
C13	0.0220 (6)	0.0227 (6)	0.0221 (6)	−0.0051 (5)	0.0011 (5)	0.0019 (5)
C14	0.0256 (6)	0.0243 (6)	0.0179 (6)	−0.0035 (5)	0.0021 (5)	0.0003 (5)
C15	0.0228 (6)	0.0245 (6)	0.0209 (6)	−0.0046 (5)	0.0025 (5)	0.0026 (5)
C16	0.0272 (7)	0.0242 (7)	0.0275 (7)	−0.0023 (5)	0.0035 (5)	−0.0022 (5)
C17	0.0350 (7)	0.0323 (7)	0.0208 (6)	−0.0054 (6)	0.0040 (5)	−0.0063 (5)
C18	0.0300 (7)	0.0296 (7)	0.0192 (6)	−0.0061 (6)	−0.0006 (5)	0.0013 (5)
C19	0.0233 (6)	0.0263 (6)	0.0234 (6)	−0.0015 (5)	0.0012 (5)	0.0042 (5)
O1A	0.0408 (6)	0.0263 (5)	0.0234 (5)	0.0027 (4)	0.0073 (4)	−0.0045 (4)
O2A	0.0453 (6)	0.0211 (5)	0.0281 (5)	0.0023 (4)	0.0044 (4)	−0.0010 (4)
N1A	0.0245 (5)	0.0213 (5)	0.0182 (5)	0.0002 (4)	0.0012 (4)	0.0006 (4)
C1A	0.0265 (6)	0.0218 (6)	0.0173 (6)	−0.0001 (5)	−0.0032 (5)	−0.0007 (5)
C2A	0.0265 (6)	0.0238 (6)	0.0185 (6)	0.0031 (5)	−0.0024 (5)	−0.0005 (5)
C3A	0.0255 (6)	0.0216 (6)	0.0172 (6)	−0.0013 (5)	−0.0006 (5)	−0.0015 (5)
C4A	0.0227 (6)	0.0235 (6)	0.0182 (6)	0.0021 (5)	−0.0001 (5)	0.0001 (5)
C5A	0.0302 (7)	0.0237 (6)	0.0174 (6)	0.0018 (5)	−0.0004 (5)	−0.0019 (5)
C6A	0.0285 (7)	0.0303 (7)	0.0186 (6)	−0.0033 (5)	−0.0040 (5)	0.0007 (5)
C7A	0.0255 (7)	0.0325 (7)	0.0200 (6)	0.0040 (6)	−0.0016 (5)	0.0037 (5)
C8A	0.0303 (7)	0.0215 (6)	0.0199 (6)	0.0025 (5)	−0.0001 (5)	0.0012 (5)
C9A	0.0331 (7)	0.0271 (7)	0.0193 (6)	−0.0029 (6)	0.0003 (5)	0.0024 (5)
C10A	0.0289 (7)	0.0310 (7)	0.0185 (6)	−0.0001 (6)	0.0013 (5)	0.0004 (5)
C11A	0.0397 (8)	0.0312 (7)	0.0195 (6)	−0.0004 (6)	0.0022 (6)	0.0035 (5)

Geometric parameters (Å, º) top

O1—C1	1.2142 (16)	C15—C19	1.5162 (18)
O2—C2	1.2137 (16)	C16—H16	0.9500
N1—C1	1.3895 (17)	C16—C17	1.389 (2)
N1—C2	1.3861 (16)	C17—H17	0.9500
N1—C12	1.4662 (17)	C17—C18	1.387 (2)
C1—C3	1.5141 (18)	C18—H18	0.9500
C2—C4	1.5122 (18)	C19—H19A	0.9900
C3—H3	1.0000	C19—H19B	0.9900
C3—C4	1.5458 (17)	C19—N1A	1.4640 (17)
C3—C8	1.5605 (18)	O1A—C1A	1.2098 (17)
C4—H4	1.0000	O2A—C2A	1.2127 (17)
C4—C5	1.5548 (18)	N1A—C1A	1.3845 (17)
C5—H5	1.0000	N1A—C2A	1.3834 (17)
C5—C6	1.5052 (18)	C1A—C3A	1.5093 (18)
C5—C10	1.5334 (18)	C2A—C4A	1.5110 (19)
C6—H6	0.9500	C3A—H3A	1.0000
C6—C7	1.333 (2)	C3A—C4A	1.5415 (18)
C7—H7	0.9500	C3A—C8A	1.5606 (18)
C7—C8	1.5065 (19)	C4A—H4A	1.0000
C8—H8	1.0000	C4A—C5A	1.5596 (17)
C8—C9	1.5373 (19)	C5A—H5A	1.0000
C9—H9	1.0000	C5A—C6A	1.499 (2)
C9—C10	1.5108 (18)	C5A—C10A	1.5336 (19)
C9—C11	1.5095 (19)	C6A—H6A	0.9500
C10—H10	1.0000	C6A—C7A	1.330 (2)
C10—C11	1.509 (2)	C7A—H7A	0.9500
C11—H11A	0.9900	C7A—C8A	1.505 (2)
C11—H11B	0.9900	C8A—H8A	1.0000
C12—H12A	0.9900	C8A—C9A	1.5335 (19)
C12—H12B	0.9900	C9A—H9A	1.0000
C12—C13	1.5149 (19)	C9A—C10A	1.511 (2)
C13—C14	1.3958 (18)	C9A—C11A	1.5035 (18)
C13—C18	1.3938 (19)	C10A—H10A	1.0000
C14—H14	0.9500	C10A—C11A	1.512 (2)
C14—C15	1.3984 (19)	C11A—H11C	0.9900
C15—C16	1.3930 (19)	C11A—H11D	0.9900

C1—N1—C12	123.91 (11)	C15—C16—H16	119.9
C2—N1—C1	113.28 (11)	C17—C16—C15	120.18 (14)
C2—N1—C12	122.80 (11)	C17—C16—H16	119.9
O1—C1—N1	123.80 (13)	C16—C17—H17	119.8
O1—C1—C3	127.65 (12)	C18—C17—C16	120.38 (13)
N1—C1—C3	108.55 (10)	C18—C17—H17	119.8
O2—C2—N1	124.02 (12)	C13—C18—H18	119.8
O2—C2—C4	127.39 (12)	C17—C18—C13	120.32 (13)
N1—C2—C4	108.59 (11)	C17—C18—H18	119.8
C1—C3—H3	109.9	C15—C19—H19A	108.7
C1—C3—C4	104.68 (10)	C15—C19—H19B	108.7
C1—C3—C8	113.41 (10)	H19A—C19—H19B	107.6
C4—C3—H3	109.9	N1A—C19—C15	114.09 (11)
C4—C3—C8	109.03 (10)	N1A—C19—H19A	108.7
C8—C3—H3	109.9	N1A—C19—H19B	108.7
C2—C4—C3	104.89 (10)	C1A—N1A—C19	123.74 (11)
C2—C4—H4	109.8	C2A—N1A—C19	123.18 (11)
C2—C4—C5	112.34 (10)	C2A—N1A—C1A	112.90 (11)
C3—C4—H4	109.8	O1A—C1A—N1A	123.87 (13)
C3—C4—C5	110.02 (10)	O1A—C1A—C3A	127.44 (12)
C5—C4—H4	109.8	N1A—C1A—C3A	108.67 (11)
C4—C5—H5	111.5	O2A—C2A—N1A	123.57 (13)
C6—C5—C4	107.40 (10)	O2A—C2A—C4A	127.37 (12)
C6—C5—H5	111.5	N1A—C2A—C4A	109.05 (11)
C6—C5—C10	110.16 (11)	C1A—C3A—H3A	110.3
C10—C5—C4	104.41 (10)	C1A—C3A—C4A	104.98 (10)
C10—C5—H5	111.5	C1A—C3A—C8A	111.61 (11)
C5—C6—H6	122.8	C4A—C3A—H3A	110.3
C7—C6—C5	114.43 (12)	C4A—C3A—C8A	109.21 (10)
C7—C6—H6	122.8	C8A—C3A—H3A	110.3
C6—C7—H7	122.6	C2A—C4A—C3A	104.35 (10)
C6—C7—C8	114.78 (12)	C2A—C4A—H4A	110.1
C8—C7—H7	122.6	C2A—C4A—C5A	111.89 (11)
C3—C8—H8	111.7	C3A—C4A—H4A	110.1
C7—C8—C3	107.44 (11)	C3A—C4A—C5A	110.04 (10)
C7—C8—H8	111.7	C5A—C4A—H4A	110.1
C7—C8—C9	109.73 (11)	C4A—C5A—H5A	111.7
C9—C8—C3	104.14 (10)	C6A—C5A—C4A	106.52 (11)
C9—C8—H8	111.7	C6A—C5A—H5A	111.7
C8—C9—H9	116.8	C6A—C5A—C10A	109.76 (11)
C10—C9—C8	110.98 (11)	C10A—C5A—C4A	105.14 (11)
C10—C9—H9	116.8	C10A—C5A—H5A	111.7
C11—C9—C8	121.91 (12)	C5A—C6A—H6A	122.7
C11—C9—H9	116.8	C7A—C6A—C5A	114.54 (13)
C11—C9—C10	59.94 (9)	C7A—C6A—H6A	122.7
C5—C10—H10	117.2	C6A—C7A—H7A	122.5
C9—C10—C5	110.05 (11)	C6A—C7A—C8A	115.08 (13)
C9—C10—H10	117.2	C8A—C7A—H7A	122.5
C11—C10—C5	121.46 (12)	C3A—C8A—H8A	111.8
C11—C10—C9	59.99 (9)	C7A—C8A—C3A	107.58 (11)
C11—C10—H10	117.2	C7A—C8A—H8A	111.8
C9—C11—H11A	117.8	C7A—C8A—C9A	109.53 (11)
C9—C11—H11B	117.8	C9A—C8A—C3A	103.86 (11)
C10—C11—C9	60.07 (9)	C9A—C8A—H8A	111.8
C10—C11—H11A	117.8	C8A—C9A—H9A	116.8
C10—C11—H11B	117.8	C10A—C9A—C8A	110.82 (11)
H11A—C11—H11B	114.9	C10A—C9A—H9A	116.8
N1—C12—H12A	109.0	C11A—C9A—C8A	121.91 (13)
N1—C12—H12B	109.0	C11A—C9A—H9A	116.8
N1—C12—C13	112.89 (11)	C11A—C9A—C10A	60.24 (9)
H12A—C12—H12B	107.8	C5A—C10A—H10A	117.0
C13—C12—H12A	109.0	C9A—C10A—C5A	110.41 (11)
C13—C12—H12B	109.0	C9A—C10A—H10A	117.0
C14—C13—C12	120.23 (12)	C9A—C10A—C11A	59.65 (9)
C18—C13—C12	120.68 (12)	C11A—C10A—C5A	121.92 (13)
C18—C13—C14	119.09 (13)	C11A—C10A—H10A	117.0
C13—C14—H14	119.6	C9A—C11A—C10A	60.11 (9)
C13—C14—C15	120.87 (12)	C9A—C11A—H11C	117.8
C15—C14—H14	119.6	C9A—C11A—H11D	117.8
C14—C15—C19	120.48 (12)	C10A—C11A—H11C	117.8
C16—C15—C14	119.15 (12)	C10A—C11A—H11D	117.8
C16—C15—C19	120.31 (13)	H11C—C11A—H11D	114.9

O1—C1—C3—C4	179.09 (13)	C14—C15—C16—C17	−1.2 (2)
O1—C1—C3—C8	−62.18 (18)	C14—C15—C19—N1A	−76.21 (16)
O2—C2—C4—C3	178.79 (13)	C15—C16—C17—C18	1.2 (2)
O2—C2—C4—C5	59.30 (17)	C15—C19—N1A—C1A	−97.03 (15)
N1—C1—C3—C4	−0.66 (14)	C15—C19—N1A—C2A	88.29 (15)
N1—C1—C3—C8	118.07 (11)	C16—C15—C19—N1A	106.82 (14)
N1—C2—C4—C3	−0.93 (14)	C16—C17—C18—C13	−0.2 (2)
N1—C2—C4—C5	−120.42 (11)	C18—C13—C14—C15	0.7 (2)
N1—C12—C13—C14	−83.59 (15)	C19—C15—C16—C17	175.77 (13)
N1—C12—C13—C18	95.83 (15)	C19—N1A—C1A—O1A	4.3 (2)
C1—N1—C2—O2	−179.17 (13)	C19—N1A—C1A—C3A	−174.23 (11)
C1—N1—C2—C4	0.56 (15)	C19—N1A—C2A—O2A	−2.9 (2)
C1—N1—C12—C13	95.96 (15)	C19—N1A—C2A—C4A	175.83 (11)
C1—C3—C4—C2	0.94 (13)	O1A—C1A—C3A—C4A	179.52 (13)
C1—C3—C4—C5	121.97 (11)	O1A—C1A—C3A—C8A	−62.29 (18)
C1—C3—C8—C7	−61.47 (13)	O2A—C2A—C4A—C3A	176.86 (14)
C1—C3—C8—C9	−177.84 (10)	O2A—C2A—C4A—C5A	57.92 (19)
C2—N1—C1—O1	−179.68 (13)	N1A—C1A—C3A—C4A	−2.04 (14)
C2—N1—C1—C3	0.08 (15)	N1A—C1A—C3A—C8A	116.15 (12)
C2—N1—C12—C13	−84.97 (15)	N1A—C2A—C4A—C3A	−1.85 (14)
C2—C4—C5—C6	61.26 (13)	N1A—C2A—C4A—C5A	−120.80 (12)
C2—C4—C5—C10	178.23 (10)	C1A—N1A—C2A—O2A	−178.14 (13)
C3—C4—C5—C6	−55.19 (13)	C1A—N1A—C2A—C4A	0.63 (15)
C3—C4—C5—C10	61.77 (12)	C1A—C3A—C4A—C2A	2.29 (13)
C3—C8—C9—C10	62.45 (13)	C1A—C3A—C4A—C5A	122.48 (11)
C3—C8—C9—C11	129.29 (12)	C1A—C3A—C8A—C7A	−62.90 (14)
C4—C3—C8—C7	54.72 (13)	C1A—C3A—C8A—C9A	−178.96 (11)
C4—C3—C8—C9	−61.65 (12)	C2A—N1A—C1A—O1A	179.45 (13)
C4—C5—C6—C7	57.67 (15)	C2A—N1A—C1A—C3A	0.93 (15)
C4—C5—C10—C9	−62.34 (13)	C2A—C4A—C5A—C6A	58.52 (14)
C4—C5—C10—C11	−128.70 (12)	C2A—C4A—C5A—C10A	174.98 (11)
C5—C6—C7—C8	0.46 (18)	C3A—C4A—C5A—C6A	−57.00 (14)
C5—C10—C11—C9	96.36 (13)	C3A—C4A—C5A—C10A	59.46 (14)
C6—C5—C10—C9	52.70 (14)	C3A—C8A—C9A—C10A	62.70 (14)
C6—C5—C10—C11	−13.66 (16)	C3A—C8A—C9A—C11A	129.81 (13)
C6—C7—C8—C3	−58.46 (15)	C4A—C3A—C8A—C7A	52.73 (14)
C6—C7—C8—C9	54.16 (16)	C4A—C3A—C8A—C9A	−63.33 (13)
C7—C8—C9—C10	−52.31 (14)	C4A—C5A—C6A—C7A	58.06 (15)
C7—C8—C9—C11	14.54 (17)	C4A—C5A—C10A—C9A	−61.42 (14)
C8—C3—C4—C2	−120.71 (11)	C4A—C5A—C10A—C11A	−127.63 (13)
C8—C3—C4—C5	0.32 (14)	C5A—C6A—C7A—C8A	0.41 (17)
C8—C9—C10—C5	0.10 (15)	C5A—C10A—C11A—C9A	96.39 (14)
C8—C9—C10—C11	115.61 (13)	C6A—C5A—C10A—C9A	52.79 (14)
C8—C9—C11—C10	−97.29 (13)	C6A—C5A—C10A—C11A	−13.42 (17)
C10—C5—C6—C7	−55.47 (16)	C6A—C7A—C8A—C3A	−58.00 (15)
C11—C9—C10—C5	−115.51 (13)	C6A—C7A—C8A—C9A	54.27 (15)
C12—N1—C1—O1	−0.5 (2)	C7A—C8A—C9A—C10A	−51.98 (15)
C12—N1—C1—C3	179.24 (12)	C7A—C8A—C9A—C11A	15.13 (18)
C12—N1—C2—O2	1.7 (2)	C8A—C3A—C4A—C2A	−117.51 (11)
C12—N1—C2—C4	−178.61 (11)	C8A—C3A—C4A—C5A	2.69 (15)
C12—C13—C14—C15	−179.88 (12)	C8A—C9A—C10A—C5A	−0.12 (16)
C12—C13—C18—C17	179.82 (13)	C8A—C9A—C10A—C11A	115.72 (14)
C13—C14—C15—C16	0.3 (2)	C8A—C9A—C11A—C10A	−97.25 (15)
C13—C14—C15—C19	−176.71 (12)	C10A—C5A—C6A—C7A	−55.27 (15)
C14—C13—C18—C17	−0.8 (2)	C11A—C9A—C10A—C5A	−115.84 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···O2Aⁱ	1.00	2.53	3.3958 (17)	144
C9A—H9A···O2Aⁱ	1.00	2.51	3.3041 (17)	136
C9—H9···O1Aⁱⁱ	1.00	2.41	3.1985 (17)	135
C7A—H7A···O2Aⁱⁱⁱ	0.95	2.52	3.1135 (18)	121

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z+1/2.

Acknowledgements

We are grateful to GVSU's Weldon Fund for financial support of this work. We thank Dr Randy Winchester (GVSU) for sharing these experiments with the Fall 2024 CHM 480 course, Dr Stephanie Billinovich (GVSU) for help with instrumentation, and Brianna Gordon for her wisdom and support as a TA for this course.

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