The co-crystal 4,6-di­acetyl­resorcinol–1-amino­pyrene (2/1)

Magrashi, M.A.; Aazam, E.S.

doi:10.1107/S2056989022005588

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Volume 78| Part 6| June 2022| Pages 679-681

https://doi.org/10.1107/S2056989022005588

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The co-crystal 4,6-diacetylresorcinol–1-aminopyrene (2/1)

Maryam Ali Magrashi ^a and Elham Shafik Aazam ^a ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 23622, Saudi Arabia
^*Correspondence e-mail: eazam@kau.edu.sa

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 26 April 2022; accepted 22 May 2022; online 31 May 2022)

The structure of the title molecular complex, C₁₆H₁₁N·2C₁₀H₁₀O₄, at 150 K has been determined. The molecules form stacks consisting of aggregates with disordered 1-aminopyrene molecule surrounded by two 4,6-diacetylresorcinol molecules. Neighbouring stacks are linked by hydrogen bonds between the amine H atoms of the 1-aminopyrene molecule with the adjacent carbonyl oxygen atom of the 4,6-diacetylresorcinol molecule.

Keywords: crystal structure; co-crystal; hydrogen bonds; stacking interactions; disorder.

CCDC reference: 2174187

1. Chemical context

Co-crystals are crystalline single phase materials made up of molecules of two or more compounds. They are used in a variety of fields, including paper, textiles and the chemical, photographic, and electronic industries (Golbedaghi & Fausto, 2018 ). However, their main uses are centered in the pharmaceutical industry, where they have been gaining importance in recent years.

Schiff bases are the products of the condensation reaction of aldehydes or ketones with amines. They have multiple uses, for example as pigments and dyes, intermediates in organic synthesis, and as catalysts and polymer stabilizers. They also exhibit a broad range of biological activities. They play an important role in coordination chemistry as they readily form stable complexes with most transition metals (Aazam et al., 2006 , 2008 , 2010 ; El-Attar & Aazam, 2021 ). In the process of the synthesis of such compounds with 4,6-diacetylresorcinol and 1-aminopyrene as the precursors, a new co-crystal, C₁₆H₁₁N·2C₁₀H₁₀O₄, has been obtained.

2. Structural commentary

The formula unit of the title compound consists of two 4,6-diacetylresorcinol molecules and one 1-aminopyrene molecule, which lies on an inversion center. Besides this, this molecule is further disordered so that the amino N atom is distributed over four chemically equivalent positions, at the C11 and C13 atoms, with the occupancies of 0.428 (2) and 0.072 (2) for N1 and N1B, respectively (Fig. 1).

Figure 1
The asymmetric unit of the title compound with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the 4,6-diacetylresorcinol molecule, the hydroxy groups form intramolecular hydrogen bonds with the oxygen atoms of neighbouring acetyl groups, generating S(6) rings (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.85 (3)	1.80 (3)	2.545 (2)	146 (2)
O3—H3⋯O4	0.84 (2)	1.80 (2)	2.542 (2)	147 (2)
N1—H1A⋯O3ⁱ	0.88 (1)	2.30 (2)	3.131 (3)	156 (4)
N1—H1B⋯O1	0.88 (1)	2.16 (2)	2.966 (3)	154 (3)
N1B—H1C⋯O2ⁱⁱ	0.88 (1)	2.05 (6)	2.902 (18)	162 (17)
N1B—H1D⋯O4ⁱⁱⁱ	0.88 (1)	1.89 (6)	2.731 (18)	159 (14)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) x, y, z+1.

3. Supramolecular features

In the crystal, the molecules form centrosymmetric aggregates with two molecules of 4,6-diacetylresorcinol positioned on both sides of the 1-aminopyrene molecule (Fig. 2). The mean planes of the aromatic rings of the 4,6-diacetylresorcinol molecules are inclined at 2.91 (10)° to the mean plane of the tetracyclic core of the 1-aminopyrene molecule. A short intercentroid separation Cg1⋯Cg2 of 3.492 (1) Å is observed in this aggregate, with Cg1 being the centroid of C3–C8 ring of diacetylresorcinol and Cg2 the centroid of one of the aminopyrene rings, C11–C18. These aggregates are packed into stacks by π–π stacking interactions between 4,6-diacetylresorcinol molecules. Neighbouring stacks are linked by hydrogen bonds between the amino H atom of the 1-aminopyrene molecule with the adjacent carbonyl oxygen atom of the 4,6-diacetylresorcinol molecule, thus forming a three-dimensional network (Fig. 3).

Figure 2
A view of the crystal packing showing the π–π stacking interactions.

Figure 3
The crystal packing of the title compound viewed along the b axis, showing the N—H⋯O hydrogen bonds.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42; May 2021; Groom et al., 2016 ) gave the structures of the individual components. In the structure of 4,6-diacetylresorcinol (Kokila et al., 1992 , refcode VOXPED) the molecule is almost planar, with the oxygen atoms of the acetyl groups deviating by 0.074 (1) and 0.072 (2) Å from the mean plane of the benzene ring. There are intramolecular hydrogen bonds between the oxygen atoms of the acetyl groups and the hydroxy hydrogen atoms. A search for 1-aminopyrene gave two hits for co-crystals composed of 1-aminopyrene molecules with either 7,7′,8,8′-tetracyanoquinodimethane or 3,5-dinitrobenzoic acid and showed that the NH₂ groups can act as H-donors in the intermolecular hydrogen-bonding interactions, as in the title compound. (Mandal et al., 2020 , refcode BOYQOY; Mandal et al., 2019 , refcode LORBOM).

5. Synthesis and crystallization

A solution of 1-aminopyrene (1 mmol, 0.233 g) dissolved in 10 ml of ethanol was added dropwise to 4,6-diacetylresorcinol (DAR) (0.5 mmol, 0.097 g) dissolved in 10 ml of ethanol, 3 drops of acetic acid were added, and the mixture was stirred for 15 min at room temperature and then for about 3 h under reflux. Yellow fiber-like crystals of the Schiff base ligand were separated. They were filtered off and washed with 4 ml of ethanol, weight = 0.021 g, yield = 7.12%, m.p. = 523 K, m/z = 592.7 (C₄₂H₂₈N₂O₂). The filtrate was left overnight upon which dark-brown rectangular co-crystals were formed, weight = 0.04 g, yield = 19.5%, m.p. = 418 K, m/z = 605.62 (C₁₆H₁₁N·2C₁₀H₁₀O₄). ¹H NMR (800 MHz, DMSO-d₆) δ 12.75 (s, br, –OH), 8.406 (s, 2H, DAR), 8.251 (d, 1H), 7.992 (d, 2H), 7.992 (d, 1H), 7.958 (d, 1H), 87.915 (d, 2H), 7.880 (m, 1H), 7.367 (d, 1H), 6.392 (s, 2H, DAR), 6.314 (s, br, NH2, 2H), 2.661 (s, Me, 12H).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C—N bond distances for the disordered N atom were restrained to be similar. The minor occupancy N1B atom was constrained to have the same ADPs as the C atom to which it is bonded. N—H bond distances were restrained to a target value of 0.88 (2) Å, and the H—N—H and C—N—H bond angles were restrained to be similar to each other. Subject to these conditions the occupancy rates refined to 0.428 (2) and 0.072 (2). O-bound H atoms were refined with U_iso(H) = 1.5U_eq(O). C-bound H atoms were positioned geometrically (C—H = 0.9–0.98 Å) and refined as riding on their parent atoms with U_iso(H) = 1.2–1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₁N·2C₁₀H₁₀O₄
M_r	605.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	18.7222 (14), 9.7870 (6), 16.9398 (15)
β (°)	113.758 (4)
V (Å³)	2840.9 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.45 × 0.26 × 0.22

Data collection
Diffractometer	Bruker AXS D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.673, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	33773, 4316, 3741
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.153, 1.15
No. of reflections	4316
No. of parameters	231
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), ShelXle (Hübschle et al., 2011 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2174187

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989022005588/yk2169sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022005588/yk2169Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022005588/yk2169Isup3.cml

checkCIF report

Computing details top

Data collection: APEX4 (Bruker, 2021); cell refinement: SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b), ShelXle (Hübschle et al., 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

4,6-Diacetylresorcinol–1-aminopyrene (2/1) top

Crystal data top

C₁₆H₁₁N·2C₁₀H₁₀O₄	F(000) = 1272
M_r = 605.62	D_x = 1.416 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.7222 (14) Å	Cell parameters from 9850 reflections
b = 9.7870 (6) Å	θ = 2.4–33.2°
c = 16.9398 (15) Å	µ = 0.10 mm⁻¹
β = 113.758 (4)°	T = 150 K
V = 2840.9 (4) Å³	Block, yellow
Z = 4	0.45 × 0.26 × 0.22 mm

Data collection top

Bruker AXS D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	4316 independent reflections
Radiation source: fine focus sealed tube X-ray source	3741 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	R_int = 0.046
Detector resolution: 7.4074 pixels mm^-1	θ_max = 30.5°, θ_min = 2.5°
ω and phi scans	h = −26→26
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.673, T_max = 0.747	l = −24→24
33773 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: mixed
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0356P)² + 4.9256P] where P = (F_o² + 2F_c²)/3
4316 reflections	(Δ/σ)_max < 0.001
231 parameters	Δρ_max = 0.35 e Å⁻³
13 restraints	Δρ_min = −0.26 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.

Refinement. The single nitrogen atom is disordered over four chemically equivalent positions (each two are also crystallographically equivalent, by inversion). The C-N bond distances were restrained to be similar. The minor N atom was constrained to have the same ADP as the C atom it is bonded to. The N-H bond distances were restrained to a target value of 0.88 (2) Angstrom, and the H-N-H and C-N-H bond angles were each restrained to be similar to each other. Subject to these conditions the occupancy rates refined to two times 0.428 (2) and two times 0.072 (2).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.65970 (9)	0.27504 (17)	0.27887 (8)	0.0435 (4)
O2	0.73863 (8)	0.46240 (16)	0.24707 (9)	0.0406 (3)
H2	0.7158 (15)	0.422 (3)	0.2746 (11)	0.061*
O3	0.73548 (7)	0.49314 (13)	−0.02964 (9)	0.0318 (3)
H3	0.7141 (13)	0.459 (2)	−0.0788 (16)	0.048*
O4	0.65513 (7)	0.32200 (14)	−0.14377 (8)	0.0333 (3)
N1	0.63242 (19)	0.2052 (3)	0.43483 (19)	0.0232 (6)	0.428 (2)
H1A	0.6785 (13)	0.167 (4)	0.462 (2)	0.028*	0.428 (2)
H1B	0.636 (3)	0.252 (3)	0.3924 (19)	0.028*	0.428 (2)
N1B	0.6296 (10)	0.2240 (18)	0.6962 (10)	0.0255 (3)	0.072 (2)
H1C	0.676 (5)	0.184 (17)	0.716 (6)	0.031*	0.072 (2)
H1D	0.625 (10)	0.261 (10)	0.741 (4)	0.031*	0.072 (2)
C1	0.63682 (10)	0.23098 (19)	0.20409 (11)	0.0303 (4)
C2	0.58258 (12)	0.1108 (2)	0.17814 (13)	0.0392 (4)
H2A	0.535960	0.134104	0.126697	0.059*
H2B	0.567315	0.086926	0.225370	0.059*
H2C	0.609006	0.032779	0.165398	0.059*
C3	0.66261 (9)	0.29590 (16)	0.14205 (9)	0.0232 (3)
C4	0.71264 (9)	0.41203 (17)	0.16646 (10)	0.0264 (3)
C5	0.73613 (9)	0.47613 (17)	0.10833 (11)	0.0265 (3)
H5	0.769710	0.553232	0.125827	0.032*
C6	0.71078 (8)	0.42813 (15)	0.02447 (10)	0.0228 (3)
C7	0.66054 (8)	0.31225 (15)	−0.00255 (9)	0.0194 (3)
C8	0.63794 (8)	0.24981 (15)	0.05741 (9)	0.0206 (3)
H8	0.604356	0.172691	0.039992	0.025*
C9	0.63396 (9)	0.26350 (17)	−0.09192 (10)	0.0242 (3)
C10	0.58093 (10)	0.1419 (2)	−0.12108 (12)	0.0339 (4)
H10A	0.568838	0.123625	−0.182006	0.051*
H10B	0.532509	0.160674	−0.113824	0.051*
H10C	0.606809	0.062098	−0.086448	0.051*
C11	0.60624 (9)	0.27031 (15)	0.48402 (10)	0.0237 (3)
H11	0.624879	0.227360	0.445699	0.028*	0.572 (2)
C12	0.63162 (9)	0.22506 (16)	0.56916 (11)	0.0283 (3)
H12	0.666448	0.149723	0.587700	0.034*
C13	0.60710 (9)	0.28760 (16)	0.62685 (10)	0.0255 (3)
H13	0.625984	0.256168	0.684761	0.031*	0.928 (2)
C14	0.55427 (8)	0.39772 (15)	0.60056 (9)	0.0207 (3)
C15	0.52761 (9)	0.46518 (16)	0.65871 (9)	0.0240 (3)
H15	0.546435	0.435794	0.717036	0.029*
C16	0.47590 (9)	0.57043 (16)	0.63217 (9)	0.0232 (3)
H16	0.458483	0.611875	0.671966	0.028*
C17	0.44718 (8)	0.61998 (15)	0.54519 (9)	0.0196 (3)
C18	0.47321 (8)	0.55597 (14)	0.48616 (9)	0.0174 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0494 (8)	0.0610 (10)	0.0232 (6)	0.0200 (7)	0.0178 (6)	0.0096 (6)
O2	0.0380 (7)	0.0502 (9)	0.0258 (6)	0.0040 (6)	0.0048 (5)	−0.0143 (6)
O3	0.0326 (6)	0.0283 (6)	0.0415 (7)	−0.0002 (5)	0.0223 (6)	0.0058 (5)
O4	0.0363 (6)	0.0425 (7)	0.0241 (6)	0.0130 (6)	0.0153 (5)	0.0058 (5)
N1	0.0294 (15)	0.0217 (14)	0.0224 (14)	0.0077 (11)	0.0147 (12)	0.0002 (11)
N1B	0.0237 (7)	0.0230 (7)	0.0254 (7)	−0.0008 (5)	0.0052 (6)	0.0077 (6)
C1	0.0299 (8)	0.0382 (9)	0.0254 (7)	0.0158 (7)	0.0137 (6)	0.0107 (7)
C2	0.0421 (10)	0.0399 (10)	0.0448 (10)	0.0109 (8)	0.0270 (9)	0.0204 (8)
C3	0.0221 (6)	0.0265 (7)	0.0211 (6)	0.0074 (5)	0.0087 (5)	0.0025 (5)
C4	0.0207 (7)	0.0296 (8)	0.0242 (7)	0.0067 (6)	0.0039 (5)	−0.0056 (6)
C5	0.0188 (6)	0.0233 (7)	0.0346 (8)	−0.0001 (5)	0.0078 (6)	−0.0063 (6)
C6	0.0176 (6)	0.0205 (6)	0.0314 (7)	0.0043 (5)	0.0111 (5)	0.0021 (6)
C7	0.0170 (6)	0.0205 (6)	0.0202 (6)	0.0038 (5)	0.0071 (5)	−0.0006 (5)
C8	0.0189 (6)	0.0194 (6)	0.0236 (7)	0.0027 (5)	0.0086 (5)	0.0001 (5)
C9	0.0211 (6)	0.0274 (7)	0.0221 (7)	0.0090 (5)	0.0067 (5)	−0.0008 (6)
C10	0.0278 (8)	0.0369 (9)	0.0321 (8)	0.0013 (7)	0.0067 (6)	−0.0151 (7)
C11	0.0222 (6)	0.0194 (6)	0.0305 (7)	−0.0009 (5)	0.0117 (6)	−0.0020 (6)
C12	0.0236 (7)	0.0205 (7)	0.0372 (9)	0.0021 (5)	0.0084 (6)	0.0054 (6)
C13	0.0237 (7)	0.0230 (7)	0.0254 (7)	−0.0008 (5)	0.0052 (6)	0.0077 (6)
C14	0.0184 (6)	0.0217 (7)	0.0205 (6)	−0.0035 (5)	0.0065 (5)	0.0032 (5)
C15	0.0240 (7)	0.0291 (8)	0.0178 (6)	−0.0041 (6)	0.0074 (5)	0.0021 (5)
C16	0.0241 (7)	0.0275 (7)	0.0190 (6)	−0.0045 (6)	0.0100 (5)	−0.0016 (5)
C17	0.0188 (6)	0.0187 (6)	0.0213 (6)	−0.0036 (5)	0.0081 (5)	−0.0010 (5)
C18	0.0157 (6)	0.0171 (6)	0.0186 (6)	−0.0036 (5)	0.0060 (5)	−0.0002 (5)

Geometric parameters (Å, º) top

O1—C1	1.240 (2)	C7—C8	1.389 (2)
O2—C4	1.3450 (19)	C7—C9	1.470 (2)
O2—H2	0.84 (3)	C8—H8	0.9500
O3—C6	1.3418 (19)	C9—C10	1.500 (2)
O3—H3	0.83 (3)	C10—H10A	0.9800
O4—C9	1.240 (2)	C10—H10B	0.9800
N1—C11	1.292 (3)	C10—H10C	0.9800
N1—H1A	0.882 (10)	C11—C12	1.396 (2)
N1—H1B	0.875 (10)	C11—C17ⁱ	1.414 (2)
N1B—C13	1.243 (14)	C11—H11	0.9500
N1B—H1C	0.882 (10)	C12—C13	1.379 (2)
N1B—H1D	0.880 (10)	C12—H12	0.9500
C1—C3	1.467 (2)	C13—C14	1.408 (2)
C1—C2	1.500 (3)	C13—H13	0.9500
C2—H2A	0.9800	C14—C18ⁱ	1.4210 (19)
C2—H2B	0.9800	C14—C15	1.432 (2)
C2—H2C	0.9800	C15—C16	1.360 (2)
C3—C8	1.392 (2)	C15—H15	0.9500
C3—C4	1.424 (2)	C16—C17	1.434 (2)
C4—C5	1.380 (2)	C16—H16	0.9500
C5—C6	1.386 (2)	C17—C18	1.4220 (19)
C5—H5	0.9500	C18—C18ⁱ	1.431 (3)
C6—C7	1.426 (2)

C4—O2—H2	109.5	O4—C9—C10	119.42 (15)
C6—O3—H3	109.5	C7—C9—C10	120.08 (14)
C11—N1—H1A	114 (2)	C9—C10—H10A	109.5
C11—N1—H1B	116 (2)	C9—C10—H10B	109.5
H1A—N1—H1B	106 (4)	H10A—C10—H10B	109.5
C13—N1B—H1C	120 (3)	C9—C10—H10C	109.5
C13—N1B—H1D	120 (3)	H10A—C10—H10C	109.5
H1C—N1B—H1D	106 (5)	H10B—C10—H10C	109.5
O1—C1—C3	120.23 (18)	N1—C11—C12	116.75 (19)
O1—C1—C2	119.14 (16)	N1—C11—C17ⁱ	123.18 (19)
C3—C1—C2	120.63 (15)	C12—C11—C17ⁱ	120.05 (14)
C1—C2—H2A	109.5	C12—C11—H11	120.0
C1—C2—H2B	109.5	C17ⁱ—C11—H11	120.0
H2A—C2—H2B	109.5	C13—C12—C11	121.28 (14)
C1—C2—H2C	109.5	C13—C12—H12	119.4
H2A—C2—H2C	109.5	C11—C12—H12	119.4
H2B—C2—H2C	109.5	N1B—C13—C12	111.3 (10)
C8—C3—C4	117.66 (14)	N1B—C13—C14	127.6 (10)
C8—C3—C1	121.95 (15)	C12—C13—C14	120.49 (14)
C4—C3—C1	120.37 (15)	C12—C13—H13	119.8
O2—C4—C5	117.95 (16)	C14—C13—H13	119.8
O2—C4—C3	120.93 (16)	C13—C14—C18ⁱ	119.12 (14)
C5—C4—C3	121.12 (14)	C13—C14—C15	122.02 (14)
C4—C5—C6	120.08 (15)	C18ⁱ—C14—C15	118.86 (13)
C4—C5—H5	120.0	C16—C15—C14	121.37 (14)
C6—C5—H5	120.0	C16—C15—H15	119.3
O3—C6—C5	118.00 (15)	C14—C15—H15	119.3
O3—C6—C7	121.48 (14)	C15—C16—C17	121.20 (14)
C5—C6—C7	120.52 (14)	C15—C16—H16	119.4
C8—C7—C6	118.10 (13)	C17—C16—H16	119.4
C8—C7—C9	122.26 (14)	C11ⁱ—C17—C18	118.88 (13)
C6—C7—C9	119.65 (14)	C11ⁱ—C17—C16	122.40 (14)
C7—C8—C3	122.53 (14)	C18—C17—C16	118.72 (13)
C7—C8—H8	118.7	C14ⁱ—C18—C17	120.17 (13)
C3—C8—H8	118.7	C14ⁱ—C18—C18ⁱ	119.80 (16)
O4—C9—C7	120.50 (15)	C17—C18—C18ⁱ	120.04 (16)

O1—C1—C3—C8	−179.71 (15)	C6—C7—C9—O4	0.3 (2)
C2—C1—C3—C8	0.3 (2)	C8—C7—C9—C10	−0.3 (2)
O1—C1—C3—C4	−1.5 (2)	C6—C7—C9—C10	−179.83 (13)
C2—C1—C3—C4	178.49 (14)	N1—C11—C12—C13	180.0 (2)
C8—C3—C4—O2	179.86 (14)	C17ⁱ—C11—C12—C13	−1.6 (2)
C1—C3—C4—O2	1.6 (2)	C11—C12—C13—N1B	173.1 (9)
C8—C3—C4—C5	−0.3 (2)	C11—C12—C13—C14	1.3 (2)
C1—C3—C4—C5	−178.61 (14)	N1B—C13—C14—C18ⁱ	−170.7 (11)
O2—C4—C5—C6	−179.90 (14)	C12—C13—C14—C18ⁱ	−0.3 (2)
C3—C4—C5—C6	0.3 (2)	N1B—C13—C14—C15	9.6 (11)
C4—C5—C6—O3	−179.61 (14)	C12—C13—C14—C15	−179.94 (14)
C4—C5—C6—C7	−0.2 (2)	C13—C14—C15—C16	−179.26 (14)
O3—C6—C7—C8	179.53 (13)	C18ⁱ—C14—C15—C16	1.1 (2)
C5—C6—C7—C8	0.1 (2)	C14—C15—C16—C17	−1.3 (2)
O3—C6—C7—C9	−1.0 (2)	C15—C16—C17—C11ⁱ	−179.63 (14)
C5—C6—C7—C9	179.64 (13)	C15—C16—C17—C18	0.6 (2)
C6—C7—C8—C3	−0.2 (2)	C11ⁱ—C17—C18—C14ⁱ	0.1 (2)
C9—C7—C8—C3	−179.68 (13)	C16—C17—C18—C14ⁱ	179.82 (13)
C4—C3—C8—C7	0.3 (2)	C11ⁱ—C17—C18—C18ⁱ	−179.52 (15)
C1—C3—C8—C7	178.53 (13)	C16—C17—C18—C18ⁱ	0.2 (2)
C8—C7—C9—O4	179.78 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.85 (3)	1.80 (3)	2.545 (2)	146 (2)
O3—H3···O4	0.84 (2)	1.80 (2)	2.542 (2)	147 (2)
N1—H1A···O3ⁱⁱ	0.88 (1)	2.30 (2)	3.131 (3)	156 (4)
N1—H1B···O1	0.88 (1)	2.16 (2)	2.966 (3)	154 (3)
N1B—H1C···O2ⁱⁱⁱ	0.88 (1)	2.05 (6)	2.902 (18)	162 (17)
N1B—H1D···O4^iv	0.88 (1)	1.89 (6)	2.731 (18)	159 (14)

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

Acknowledgements

This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer). The authors greatly acknowledge Dr Matthias Zeller for his help and support.

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