Synthesis and structure of a 1:1 cocrystal of N,N′-bis­(pyridin-3-ylmeth­yl)pyromellitic di­imide and naphthalene-2,6-di­carb­oxy­lic acid

Mbonzhe, L.; Batisai, E.

doi:10.1107/S2056989026006110

research communications

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ISSN: 2056-9890

Volume 82| Part 7| July 2026| Pages 854-857

https://doi.org/10.1107/S2056989026006110

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Synthesis and structure of a 1:1 cocrystal of N,N′-bis(pyridin-3-ylmethyl)pyromellitic diimide and naphthalene-2,6-dicarboxylic acid

Luccile Mbonzhe ^a and Eustina Batisai ^a ^*

^aUniversity of Venda, P Bag X5050, Thohoyandou, 0950, South Africa
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 14 May 2026; accepted 11 June 2026; online 23 June 2026)

In the title cocrystal, C₂₂H₁₄N₄O₄·C₁₂H₈O₄, both components are completed by crystallographic inversion symmetry and the dihedral angle between the central fused ring system and the pendant pyridine ring is 66.21 (5)°. In the extended structure, the components are linked by O—H⋯N hydrogen bonds, generating [001] chains, and the packing is consolidated by π–π stacking and C—H⋯O interactions.

Keywords: cocrystal; pyromellitic diimide; Hirshfeld surface analysis; naphthalenedicarboxylic acid.

CCDC reference: 2561484

1. Chemical context

N,N′-Bis(pyridin-3-ylmethyl)pyromellitic diimide, C₂₂H₁₄N₄O₄, (Lig1) consists of a pyromellitic diimide core linked to meta-substituted pyridyl groups via –CH₂– linkages. These rotatable linkages impart conformational flexibility, allowing Lig1 to adopt Z_C- and Z_T- modes, where Z denotes an anti orientation of the pyridyl rings, while C (cis) and T (trans) describe the relative positions of the pyridyl nitrogen atoms (Yan et al., 2010 ). The pyromellitic diimide core further promotes π–π stacking interactions, contributing to supramolecular assembly. Owing to its semi-rigid nature, Lig1 has been widely employed in the construction of metal–organic frameworks (MOFs) exhibiting diverse topologies, with potential applications in gas sorption (Li et al., 2012 ) and fluorescence (Huang et al., 2020 ; Li et al., 2018 ).

Deprotonated naphthalene dicarboxylic acid (C₁₂H₈O₄; NDC) ligands are also widely used to prepare MOFs with potential applications in gas storage, gas separation, luminescence and catalysis (Gangu et al., 2017 ). Their aromatic ring system allows for increased π–π stacking interactions, enhancing supramolecular recognition and enabling the formation of complex polymer networks.

The aim of this work was to prepare a zinc mixed-ligand MOF containing Lig1 and NDC. However, single-crystal X-ray diffraction (SCXRD) revealed that a 1:1 cocrystal of Lig1 and NDC, (I), had formed from the solvothermal reaction and we now describe its structure.

2. Structural commentary

Compound (I) crystallizes in the triclinic space group P $[\overline{1}]$ with half a molecule of Lig1 and half a molecule of NDC in the asymmetric unit (Fig. 1). Both complete molecules are generated by crystallographic inversion centres at (1/2, 1/2, 0) and (1, 1/2, 1) for the asymmetric atoms of Lig1 and NDC, respectively. The Lig1 molecule adopts a Z_T- mode and the dihedral angle between the central fused ring system and the pendant pyridine ring is 66.21 (5)°.

Figure 1
The molecular structure of (I) with displacement ellipsoids drawn at the 70% probability level. [Symmetry codes: (i) 2 − x, 1 − y, 2 − z; (ii) 1 − x, 1 − y, −z].

3. Supramolecular features

In the extended structure of (I), the NDC molecule links to Lig1 via an O1—H1⋯N9 hydrogen bond between the carboxylic acid group of NDC and the py-N of Lig1, and a secondary interaction between the Ar-H atom of Lig 1 and the C=O group of the NDC molecule (C10—H10⋯O3). These interactions result in extended chains of alternating Lig1 and NDC molecules running along the crystallographic c-axis direction (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N9	0.95 (1)	1.64 (1)	2.5806 (13)	172 (2)
C15—H15A⋯O3ⁱ	0.99	2.56	3.4073 (14)	143
C11—H11⋯O23ⁱⁱ	0.95	2.51	3.2402 (15)	134
C10—H10⋯O3ⁱⁱⁱ	0.95	2.64	3.2414 (15)	122
C11—H11⋯O3ⁱⁱⁱ	0.95	2.62	3.2207 (15)	122
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
The packing of (I) viewed down the b-axis direction.

The chains stack in the ac plane in an offset arrangement facilitated by π–π stacking interactions [centroid-to-centroid distance = 3.767 (1) Å] between the pyridyl moieties of Lig1 of adjacent chains, as well as π–π interactions [centroid-to-centroid distance = 3.761 (1) Å] between the pyromellitic moiety of Lig1 and the naphthalene moiety of NDC of adjacent chains. Additionally, the chains interact with neighboring chains via C—H⋯O interactions in the ac plane (C15—H15A⋯O3) as well as in the b-axis direction (C11—H11⋯O23) (Fig. 2).

4. Hirshfeld surface analysis

To further quantify the nature and relative contributions of intermolecular interactions within the crystal structure of (I), two-dimensional fingerprint plots were generated using CrystalExplorer (Spackman et al. 2021 ). The Hirshfeld surface was constructed from a hydrogen-bonded unit comprising one NDC and one Lig1 molecule. The breakdown of intermolecular contacts and their percentage contributions to the total Hirshfeld surface are presented in Fig. 3. The contributions follow the order O⋯H/H⋯O (32%) > H⋯H (29%) > C⋯C (14%) > C⋯H/H⋯C (13%) > N⋯H/H⋯N (5%) > C⋯O/O⋯C (2.9%). Although O⋯H/H⋯O interactions make the largest contribution to the Hirshfeld surface, these contacts are relatively long, with the closest atom–atom distance of approximately 2.3 Å, and are mainly associated with weaker C—H⋯O interactions. H⋯H contacts also contribute significantly, indicating that van der Waals interactions play an important role in consolidating the crystal structure. The C⋯C and C⋯H interactions contribute 14% and 13%, respectively, and can be attributed to π–π stacking and C-H⋯π interactions. N⋯H/H⋯N interactions, associated with O—H⋯N hydrogen bonding, contribute a smaller proportion (5%) but represent the shortest intermolecular contacts, with a closest atom–atom distance of approximately 1.6 Å.

Figure 3
Two-dimensional fingerprint plots for (I) showing the various contributions to the Hirshfeld surface.

5. Thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD)

PXRD analysis was performed to assess the bulk phase purity of (I). A comparison of the PXRD pattern of the as-synthesized sample with the simulated pattern of (I) shows good agreement, which indicates phase purity of the sample (Fig. 4). The TGA curve shows that the cocrystal decomposes at 290 °C (Fig. 5).

Figure 4
Experimental PXRD pattern of (I) (red) overlaid with the simulated pattern generated from SCXRD data (black), confirming phase purity.

Figure 5
TGA curve of (I). Decomposition starts at 290 °C.

6. Database survey

A search of the Cambridge Structural Database (CSD) (Groom et al., 2016 ) showed that Lig1 has been used mostly in the preparation of coordination complexes. Of the 20 crystal structures deposited Co [DIBBAU, DIBBEY, DIBBIC (Li et al., 2018), OWEYEV (Li et al., 2011 )], Zn [OWEYUL (Li et al., 2011), FISCEQ (Lü et al. 2005b ), PALYIL (Lü et al. 2005a )], Cd [FISCAM (Lü et al. 2005b), PADHOT (Chai et al. 2010 ), PALYUX (Lü et al. 2005a), ZAVQIZ (Li et al., 2017 ), ZAXSOI (Li et al., 2012)], Ag (QAHBEI, QAHBIM; Yan et al., 2011 ), Hg [HUHZUI (Huang et al., 2020), PEVYUL (Li et al., 2007)], Ni (HUJBAS; Huang et al., 2020) and Mn [OWEXOE (Li et al., 2011), ZAVQEV Li et al., 2017)] and one entry is a salt of protonated Lig1 and a perchlorate ion (FISBUF; Lü et al., 2005 ). The coordination complexes exhibit structural diversity, with some investigated for CO₂ sorption (Li et al., 2012) and fluorescence properties (Huang et al., 2020; Li et al., 2018). A search on the CSD for NDC produced 683 coordination complexes containing NDC either by itself or in combination with other ligands. Additionally, there are 40 hits where NDC features in cocrystals or salts.

7. Synthesis and crystallization

Lig1 was synthesized according to a reported procedure (Li et al. 2009 ). Compound (I) crystallized from a solvothermal reaction of Lig1 (10 mg, 0.025 mmol), NDC (16 mg, 0.074 mmol), and Zn(NO₃)₂·6H₂O (20 mg, 0.067 mmol) in 3 ml of N,N-dimethylformamide (DMF) at 373 K. Cream crystals of (I) formed after 3 days. The vial was then removed from the oven and washed with 2 ml of DMF.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were positioned (C—H = 0.95–0.99 Å) geometrically and refined as riding U_iso(H) = 1.2U_eq(C). The OH H atom was found in a difference map and refined with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₁₄N₄O₄·C₁₂H₈O₄
M_r	614.55
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	130
a, b, c (Å)	6.9314 (2), 8.3554 (3), 12.5463 (4)
α, β, γ (°)	79.716 (1), 80.977 (1), 74.432 (1)
V (Å³)	684.15 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.17 × 0.13

Data collection
Diffractometer	BRUKER D8 QUEST
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.650, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	23721, 3391, 3048
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.10
No. of reflections	3391
No. of parameters	211
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28
Computer programs: APEX4 and SAINT (Bruker, 2022 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ) and X-SEED (Barbour, 2020 ).

Supporting information

CCDC reference: 2561484

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026006110/hb8224sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026006110/hb8224Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989026006110/hb8224Isup3.mol

checkCIF report

Computing details top

N,N'-Bis(pyridin-3-ylmethyl)pyromellitic diimide–naphthalene-2,6-dicarboxylic acid (1/1) top

Crystal data top

C₂₂H₁₄N₄O₄·C₁₂H₈O₄	Z = 1
M_r = 614.55	F(000) = 318
Triclinic, P1	D_x = 1.492 Mg m⁻³
a = 6.9314 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3554 (3) Å	Cell parameters from 9965 reflections
c = 12.5463 (4) Å	θ = 2.6–28.3°
α = 79.716 (1)°	µ = 0.11 mm⁻¹
β = 80.977 (1)°	T = 130 K
γ = 74.432 (1)°	Block, yellow
V = 684.15 (4) Å³	0.28 × 0.17 × 0.13 mm

Data collection top

BRUKER D8 QUEST diffractometer	3391 independent reflections
Radiation source: sealed tube	3048 reflections with I > 2σ(I)
Detector resolution: 7.39 pixels mm^-1	R_int = 0.040
ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→8
T_min = 0.650, T_max = 0.746	k = −11→11
23721 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0491P)² + 0.3031P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3391 reflections	Δρ_max = 0.36 e Å⁻³
211 parameters	Δρ_min = −0.28 e Å⁻³
1 restraint

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	0.94933 (14)	0.56834 (11)	0.61477 (7)	0.0239 (2)
H1	0.887 (2)	0.6401 (17)	0.5555 (9)	0.036*
O18	0.26446 (15)	0.92395 (11)	0.09152 (7)	0.0272 (2)
O23	0.50906 (14)	0.42909 (11)	0.30621 (7)	0.0243 (2)
O3	0.94674 (14)	0.81605 (11)	0.66050 (7)	0.0233 (2)
N9	0.74937 (16)	0.76234 (12)	0.46376 (8)	0.0198 (2)
N16	0.36780 (14)	0.69532 (12)	0.22228 (8)	0.0174 (2)
C7	1.08872 (17)	0.31773 (14)	0.92125 (9)	0.0174 (2)
H7	1.139624	0.199353	0.934264	0.021*
C8	1.06660 (16)	0.39725 (14)	0.81661 (9)	0.0171 (2)
H8	1.098256	0.333481	0.757836	0.021*
C4	0.99645 (16)	0.57470 (14)	0.79612 (9)	0.0161 (2)
C2	0.96390 (16)	0.66531 (14)	0.68329 (9)	0.0175 (2)
C14	0.59674 (18)	0.72163 (14)	0.43038 (9)	0.0199 (2)
H14	0.570054	0.615645	0.459367	0.024*
C13	0.47578 (17)	0.82771 (14)	0.35519 (9)	0.0170 (2)
C15	0.30468 (17)	0.77764 (14)	0.31994 (9)	0.0188 (2)
H15B	0.252472	0.700467	0.379958	0.023*
H15A	0.193824	0.878866	0.305142	0.023*
C17	0.33909 (17)	0.77633 (14)	0.11648 (9)	0.0182 (2)
C19	0.41928 (16)	0.64345 (13)	0.04451 (9)	0.0161 (2)
C20	0.42361 (17)	0.65689 (14)	−0.06757 (9)	0.0173 (2)
H20A	0.373241	0.760065	−0.111895	0.021*
C21	0.49260 (16)	0.49242 (13)	0.10978 (9)	0.0161 (2)
C10	0.78669 (18)	0.91129 (15)	0.42350 (10)	0.0203 (2)
H10	0.893561	0.940894	0.448094	0.024*
C11	0.67585 (19)	1.02447 (15)	0.34729 (11)	0.0239 (3)
H11	0.707520	1.128836	0.318970	0.029*
C12	0.51751 (18)	0.98197 (15)	0.31325 (10)	0.0221 (2)
H12	0.438083	1.057794	0.261594	0.027*
C22	0.46261 (16)	0.52553 (14)	0.22495 (9)	0.0171 (2)
C5	0.94801 (16)	0.66816 (14)	0.88063 (9)	0.0168 (2)
H5	0.903446	0.786937	0.865789	0.020*
C6	0.96400 (16)	0.58878 (13)	0.98974 (9)	0.0157 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0342 (5)	0.0199 (4)	0.0182 (4)	−0.0031 (3)	−0.0112 (3)	−0.0029 (3)
O18	0.0375 (5)	0.0159 (4)	0.0253 (4)	0.0007 (4)	−0.0065 (4)	−0.0037 (3)
O23	0.0314 (5)	0.0212 (4)	0.0178 (4)	−0.0035 (3)	−0.0039 (3)	−0.0003 (3)
O3	0.0315 (5)	0.0200 (4)	0.0205 (4)	−0.0099 (3)	−0.0075 (3)	0.0012 (3)
N9	0.0262 (5)	0.0188 (5)	0.0152 (4)	−0.0048 (4)	−0.0051 (4)	−0.0029 (3)
N16	0.0195 (4)	0.0170 (4)	0.0165 (4)	−0.0040 (3)	−0.0025 (3)	−0.0044 (3)
C7	0.0182 (5)	0.0158 (5)	0.0183 (5)	−0.0031 (4)	−0.0025 (4)	−0.0036 (4)
C8	0.0175 (5)	0.0184 (5)	0.0160 (5)	−0.0041 (4)	−0.0015 (4)	−0.0045 (4)
C4	0.0147 (5)	0.0187 (5)	0.0152 (5)	−0.0047 (4)	−0.0029 (4)	−0.0015 (4)
C2	0.0156 (5)	0.0204 (5)	0.0168 (5)	−0.0048 (4)	−0.0027 (4)	−0.0021 (4)
C14	0.0280 (6)	0.0173 (5)	0.0154 (5)	−0.0077 (4)	−0.0035 (4)	−0.0013 (4)
C13	0.0189 (5)	0.0170 (5)	0.0149 (5)	−0.0033 (4)	−0.0004 (4)	−0.0050 (4)
C15	0.0188 (5)	0.0206 (5)	0.0179 (5)	−0.0047 (4)	−0.0003 (4)	−0.0067 (4)
C17	0.0194 (5)	0.0171 (5)	0.0187 (5)	−0.0043 (4)	−0.0030 (4)	−0.0039 (4)
C19	0.0160 (5)	0.0143 (5)	0.0184 (5)	−0.0041 (4)	−0.0024 (4)	−0.0026 (4)
C20	0.0188 (5)	0.0145 (5)	0.0182 (5)	−0.0038 (4)	−0.0035 (4)	−0.0008 (4)
C21	0.0162 (5)	0.0162 (5)	0.0166 (5)	−0.0053 (4)	−0.0026 (4)	−0.0015 (4)
C10	0.0217 (5)	0.0205 (5)	0.0203 (5)	−0.0062 (4)	−0.0028 (4)	−0.0051 (4)
C11	0.0266 (6)	0.0168 (5)	0.0289 (6)	−0.0074 (4)	−0.0060 (5)	0.0008 (4)
C12	0.0229 (6)	0.0177 (5)	0.0243 (6)	−0.0032 (4)	−0.0059 (4)	0.0007 (4)
C22	0.0169 (5)	0.0167 (5)	0.0183 (5)	−0.0049 (4)	−0.0020 (4)	−0.0032 (4)
C5	0.0173 (5)	0.0161 (5)	0.0171 (5)	−0.0041 (4)	−0.0033 (4)	−0.0014 (4)
C6	0.0141 (5)	0.0167 (5)	0.0167 (5)	−0.0036 (4)	−0.0023 (4)	−0.0030 (4)

Geometric parameters (Å, º) top

O1—C2	1.3135 (14)	C13—C12	1.3900 (16)
O1—H1	0.9501 (10)	C13—C15	1.5080 (15)
O18—C17	1.2073 (14)	C15—H15B	0.9900
O23—C22	1.2094 (14)	C15—H15A	0.9900
O3—C2	1.2182 (14)	C17—C19	1.4921 (15)
N9—C10	1.3335 (15)	C19—C20	1.3867 (15)
N9—C14	1.3391 (15)	C19—C21	1.3924 (15)
N16—C22	1.3911 (14)	C20—C21ⁱⁱ	1.3872 (15)
N16—C17	1.3963 (14)	C20—H20A	0.9500
N16—C15	1.4619 (14)	C21—C22	1.4917 (15)
C7—C8	1.3732 (15)	C10—C11	1.3843 (17)
C7—C6ⁱ	1.4216 (15)	C10—H10	0.9500
C7—H7	0.9500	C11—C12	1.3870 (17)
C8—C4	1.4201 (15)	C11—H11	0.9500
C8—H8	0.9500	C12—H12	0.9500
C4—C5	1.3748 (15)	C5—C6	1.4179 (15)
C4—C2	1.5013 (15)	C5—H5	0.9500
C14—C13	1.3889 (16)	C6—C6ⁱ	1.422 (2)
C14—H14	0.9500

C2—O1—H1	106.8 (11)	O18—C17—C19	128.73 (11)
C10—N9—C14	118.72 (10)	N16—C17—C19	105.69 (9)
C22—N16—C17	112.33 (9)	C20—C19—C21	122.87 (10)
C22—N16—C15	123.31 (9)	C20—C19—C17	129.04 (10)
C17—N16—C15	124.37 (9)	C21—C19—C17	108.09 (10)
C8—C7—C6ⁱ	120.49 (10)	C19—C20—C21ⁱⁱ	114.62 (10)
C8—C7—H7	119.8	C19—C20—H20A	122.7
C6ⁱ—C7—H7	119.8	C21ⁱⁱ—C20—H20A	122.7
C7—C8—C4	120.09 (10)	C20ⁱⁱ—C21—C19	122.52 (10)
C7—C8—H8	120.0	C20ⁱⁱ—C21—C22	129.54 (10)
C4—C8—H8	120.0	C19—C21—C22	107.95 (9)
C5—C4—C8	120.49 (10)	N9—C10—C11	122.60 (11)
C5—C4—C2	117.92 (10)	N9—C10—H10	118.7
C8—C4—C2	121.54 (10)	C11—C10—H10	118.7
O3—C2—O1	124.33 (10)	C10—C11—C12	118.46 (11)
O3—C2—C4	121.82 (10)	C10—C11—H11	120.8
O1—C2—C4	113.81 (10)	C12—C11—H11	120.8
N9—C14—C13	122.82 (11)	C11—C12—C13	119.57 (11)
N9—C14—H14	118.6	C11—C12—H12	120.2
C13—C14—H14	118.6	C13—C12—H12	120.2
C14—C13—C12	117.83 (11)	O23—C22—N16	125.12 (10)
C14—C13—C15	121.26 (10)	O23—C22—C21	128.96 (10)
C12—C13—C15	120.91 (10)	N16—C22—C21	105.93 (9)
N16—C15—C13	111.95 (9)	C4—C5—C6	120.56 (10)
N16—C15—H15B	109.2	C4—C5—H5	119.7
C13—C15—H15B	109.2	C6—C5—H5	119.7
N16—C15—H15A	109.2	C5—C6—C7ⁱ	121.66 (10)
C13—C15—H15A	109.2	C5—C6—C6ⁱ	118.99 (12)
H15B—C15—H15A	107.9	C7ⁱ—C6—C6ⁱ	119.35 (12)
O18—C17—N16	125.59 (11)

C6ⁱ—C7—C8—C4	1.93 (17)	C17—C19—C20—C21ⁱⁱ	−179.30 (11)
C7—C8—C4—C5	−0.73 (17)	C20—C19—C21—C20ⁱⁱ	0.13 (19)
C7—C8—C4—C2	−177.93 (10)	C17—C19—C21—C20ⁱⁱ	179.46 (10)
C5—C4—C2—O3	18.94 (16)	C20—C19—C21—C22	−179.81 (10)
C8—C4—C2—O3	−163.79 (11)	C17—C19—C21—C22	−0.48 (12)
C5—C4—C2—O1	−158.88 (10)	C14—N9—C10—C11	−1.02 (18)
C8—C4—C2—O1	18.39 (15)	N9—C10—C11—C12	1.23 (19)
C10—N9—C14—C13	0.25 (17)	C10—C11—C12—C13	−0.65 (18)
N9—C14—C13—C12	0.28 (17)	C14—C13—C12—C11	−0.06 (17)
N9—C14—C13—C15	−179.75 (10)	C15—C13—C12—C11	179.98 (11)
C22—N16—C15—C13	83.09 (13)	C17—N16—C22—O23	177.96 (11)
C17—N16—C15—C13	−97.45 (12)	C15—N16—C22—O23	−2.52 (18)
C14—C13—C15—N16	−92.23 (12)	C17—N16—C22—C21	−1.83 (12)
C12—C13—C15—N16	87.73 (13)	C15—N16—C22—C21	177.69 (9)
C22—N16—C17—O18	−178.33 (12)	C20ⁱⁱ—C21—C22—O23	1.7 (2)
C15—N16—C17—O18	2.15 (19)	C19—C21—C22—O23	−178.40 (12)
C22—N16—C17—C19	1.54 (12)	C20ⁱⁱ—C21—C22—N16	−178.55 (11)
C15—N16—C17—C19	−177.97 (10)	C19—C21—C22—N16	1.39 (12)
O18—C17—C19—C20	−1.4 (2)	C8—C4—C5—C6	−1.07 (16)
N16—C17—C19—C20	178.69 (11)	C2—C4—C5—C6	176.22 (10)
O18—C17—C19—C21	179.28 (12)	C4—C5—C6—C7ⁱ	−178.81 (10)
N16—C17—C19—C21	−0.59 (12)	C4—C5—C6—C6ⁱ	1.64 (19)
C21—C19—C20—C21ⁱⁱ	−0.12 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N9	0.95 (1)	1.64 (1)	2.5806 (13)	172 (2)
C15—H15A···O3ⁱⁱⁱ	0.99	2.56	3.4073 (14)	143
C11—H11···O23^iv	0.95	2.51	3.2402 (15)	134
C10—H10···O3^v	0.95	2.64	3.2414 (15)	122
C11—H11···O3^v	0.95	2.62	3.2207 (15)	122

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

Acknowledgements

EB thanks the National Research Foundation of South Africa for financial support. LM thanks the NRF and SASOL Foundation for a bursary.

Funding information

Funding for this research was provided by: National Research Foundation of South Africa (grant Nos. 129759, 138178).

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