Synthesis and crystal structure of 1,3-bis­{[N,N-bis­(2-hy­droxy­eth­yl)amino]­meth­yl}-5-{[(4,6-di­methyl­pyridin-2-yl)amino]­meth­yl}-2,4,6-tri­ethyl­benzene

Stapf, M.; Schmidt, U.; Seichter, W.; Mazik, M.

doi:10.1107/S2056989022007411

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 78| Part 8| August 2022| Pages 825-828

https://doi.org/10.1107/S2056989022007411

Open

access

Synthesis and crystal structure of 1,3-bis{[N,N-bis(2-hydroxyethyl)amino]methyl}-5-{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzene

Manuel Stapf,^a Ute Schmidt,^a Wilhelm Seichter ^a and Monika Mazik ^a ^*

^aInstitut für Organische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Str. 29, 09599 Freiberg/Sachsen, Germany
^*Correspondence e-mail: monika.mazik@chemie.tu-freiberg.de

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 22 April 2022; accepted 19 July 2022; online 26 July 2022)

In the crystal structure of the title compound, C₃₀H₅₀N₄O₄, the two bis(hydroxyethyl)amino moieties and the 2,4-dimethylpyridinylamino unit of the molecule are located on one side of the central benzene ring, while the ethyl substituents are oriented in the opposite direction. The dihedral angle between the planes of the aromatic rings is 73.6 (1)°. The conformation of the molecule is stabilized by intramolecular O—H⋯O (1.86–2.12 Å) and C—H⋯N (2.40, 2.54 Å) hydrogen bonds. Dimers of inversion-related molecules represent the basic supramolecular entities of the crystal structure. They are further connected via O—H⋯O hydrogen bonding into undulating layers extending parallel to the crystallographic bc plane. Interlayer interaction is accomplished by weak C—H⋯π contacts.

Keywords: crystal structure; tripodal molecule; O—H⋯O bonding; intramolecular hydrogen bond.

CCDC reference: 2191249

1. Chemical context

The 1,3,5-trisubstituted 2,4,6-trialkylbenzene scaffold has shown to be valuable for the construction of various artificial receptors (Hennrich & Anslyn, 2002 ). In the course of our research work, we have successfully used this molecular scaffold in the design of acyclic and macrocyclic receptors for neutral (Mazik, 2009 , 2012 ; Lippe & Mazik, 2015 ; Lippe et al., 2015 ; Amrhein et al., 2016 ; Koch et al., 2016 ; Amrhein & Mazik, 2021 ; Köhler et al., 2020 , 2021 ) and ionic substrates (Geffert et al., 2013 ; Stapf et al., 2015 ; Schulze et al., 2018 ). Our studies on the molecular recognition of carbohydrates have shown that the participation of different types of recognition groups in the complexation of the substrate favourably influences the binding process (Stapf et al., 2020a ,b ; Kaiser et al., 2019 ). Such a combination of two types of recognition units, namely heterocyclic and hydroxy groups, is realised in the triethylbenzene-based title compound 1 (see also Stapf et al., 2020a). The design of the receptors consisting of the aforementioned recognition units was inspired by the nature of the protein binding sites involved in the interactions stabilizing the crystalline protein–carbohydrate complexes (Quiocho, 1989 ). For example, 2-aminopyridine can be considered as a heterocyclic analogue of the asparagine/glutamine primary amide side chain. Furthermore, it should be noted that the formation of intramolecular interactions is also one of the factors influencing the binding properties of a receptor molecule (Rosien et al., 2013 ). Intramolecular interactions can also be observed in the crystal structure of 1.

2. Structural commentary

In the title molecule, the structure of which is shown in Fig. 1, the functionalized side arms are arranged on one side of the central benzene ring, while the ethyl substituents are oriented in the opposite direction. One of the bis(hydroxyethyl)amino moieties is disordered over two positions [s.o.f. 0.879 (2)/0.121 (2)]. The interplanar angle between the aromatic rings is 73.6 (1)°. Within the molecule, three hydroxy groups create a continuous pattern of O—H⋯O hydrogen bonds [d(H⋯O) 1.86–2.12 Å]. The amino nitrogen atoms N3 and N4 are involved in intramolecular C—H⋯N hydrogen bonding [d(H⋯N) 2.40, 2.54 Å]. The crystal structure contains four potentially solvent-accessible voids with a total volume of 110 Å³ per unit cell (Spek, 2015 ). The void volume of 27.5 Å³ and the maximum residual electron density of 0.55 e Å⁻³ indicate that the voids could be partially occupied by water molecules.

Figure 1
Perspective view of the molecular structure of the title compound including atom numbering. Anisotropic displacement ellipsoids are drawn at a 50% probability level. Dashed lines represent hydrogen-bonding interactions. For the sake of clarity, only the major position of the disordered bis(hydroxyethyl)amino moiety is shown.

3. Supramolecular features

As depicted in Fig. 2 and Fig. 3, the crystal structure is constructed of inversion-symmetric molecular dimers held together by O—H⋯N and N—H⋯O hydrogen bonding [d(H⋯N) 1.89 (2) Å; d(H⋯O) 2.19 (2) Å; graph set R₂²(6) (Etter, 1990 ; Bernstein et al., 1995 )]. These dimers are further assembled via O—H⋯O [d(H⋯O) 1.99 (2) Å] and C—H⋯O [d(H⋯O) 2.45 Å] bonds (Desiraju & Steiner, 1999 ) into layers extending parallel to the crystallographic bc plane (Fig. 4). As the layer surfaces are defined by the ethyl groups of the molecules, interlayer association is restricted to weak C—H⋯π contacts (Nishio et al., 1995 ). Information regarding non-covalent bonding present in the crystal is found in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H2A⋯O4ⁱ	0.84	1.99	2.763 (18)	152
O1A—H1A⋯N2ⁱⁱ	0.84	1.99	2.832 (12)	178
C18A—H18D⋯O2A	0.99	2.46	3.08 (2)	120
O2—H2⋯O3ⁱ	0.87 (2)	1.99 (2)	2.828 (2)	162 (3)
O1—H1⋯N2ⁱⁱ	0.87 (2)	1.89 (2)	2.7449 (19)	167 (3)
N1—H1N⋯O1ⁱⁱ	0.89 (2)	2.19 (2)	3.014 (2)	152.0 (17)
C22—H22A⋯N4	0.99	2.40	3.152 (2)	132
C18—H18A⋯O2	0.99	2.39	3.106 (3)	128
C15—H15A⋯N3	0.99	2.54	3.282 (3)	131
C13—H13A⋯O2Aⁱⁱⁱ	0.98	2.33	3.220 (14)	151
C10—H10⋯O4^iv	0.95	2.45	3.365 (2)	161
O4—H4⋯O3	0.86 (2)	2.12 (2)	2.9200 (18)	155 (3)
O3—H3⋯O1A	0.87 (2)	1.93 (2)	2.727 (13)	152 (3)
O3—H3⋯O1	0.87 (2)	1.86 (2)	2.7156 (19)	172 (3)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iv) .

Figure 2
Structure of the molecular dimer including the numbering of atoms involved in hydrogen-bonding interactions. For the sake of clarity, only the major position of the disordered hydroxyethyl moiety is shown. Hydrogen bonds are shown as dashed lines.

Figure 3
Packing excerpt of the title compound with numbering of coordinating atoms. Oxygen atoms are displayed as red, nitrogen atoms as blue circles. Hydrogen atoms excluded from intermolecular interactions are omitted for clarity. Hydrogen bonds are shown as broken lines.

Figure 4
Packing diagram of the title compound viewed down the c axis. Oxygen atoms are displayed as red, nitrogen atoms as blue circles. Hydrogen-bonding interactions are shown as dashed lines.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.43, update November 2021; Groom et al., 2016 ) for 2,4,6-triethylbenzene derivatives bearing the (4,6-dimethylpyridin-2-yl)aminomethyl unit gave eight hits. In the crystal structures of the monohydrate and the methanol solvate of {1-[(3,5-bis{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzyl)amino]cyclopentyl}methanol (CADTAG, CADTEK; Stapf et al., 2020a), the host molecules reveal similar geometries with an alternating arrangement of the substituents above and below the plane of the central benzene ring. The crystals of these solvates are composed of inversion-symmetric dimers of 1:1 host–guest complexes held together by O—H⋯N and N—H⋯O hydrogen bonds.

In the case of the ethanol solvate of 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene (RAJZAE; Mazik et al., 2004 ), dimers of host–guest units stabilized by O—H⋯N_pyr and N—H⋯O bonds represent the basic supramolecular aggregates. The latter compound is also capable of forming crystalline complexes with methyl β-D-glucopyranoside (LAJZOP; Köhler et al., 2020). This crystal structure (acetonitrile tetrasolvate monohydrate) contains two structurally different 2:1 receptor-carbohydrate complexes in which the sugar substrate is located in a cavity formed by the functionalized side arms of a pair of receptor molecules.

In the crystal structure of 1-{[N-(1,10-phenanthrolin-2-ylcarbonyl)amino]methyl}-3,5-bis{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzene (ROKJEH; Mazik et al., 2008 ), three water molecules are accommodated in the binding pocket created by the heterocyclic units (one phenanthrolinyl and two pyridinyl groups) of the host molecule. This host–water aggregate is stabilized by O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds. In a similar way, two water molecules and one ethanol molecule are accommodated in the binding pocket of 1,3-bis{[N-(1,10-phenanthrolin-2-ylcarbonyl)amino]methyl}-5-{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzene (TUGVEX; Mazik et al., 2009 ), containing one pyridinyl and two phenanthrolinyl groups.

5. Synthesis and crystallization

A mixture of diethanolamine (0.18 mL, 0.20 g, 1.88 mmol), THF (10 mL) and potassium carbonate (86 mg, 0.62 mmol) was stirred at room temperature for 30 minutes. After that, a solution of 1,3-bis(bromomethyl)-5-{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylbenzene (150 mg, 0.31 mmol) in 10 mL of THF/CH₃CN (1:1) was added dropwise and the resulting mixture was stirred at room temperature and under light exclusion (the progress of the reaction was monitored by TLC). After filtration, the solvents were removed under reduced pressure and the residual yellow oil was treated with a THF/water mixture. Then the THF was evaporated and the resulting oil was separated from the water. The oil was again dissolved in THF and dried over MgSO₄. By addition of n-hexane, the product was precipitated as a white solid (58% yield, 95 mg, 0.18 mmol). Analysis data: m.p. = 408 K; ¹H NMR (500 MHz, CDCl₃) δ 1.14 (t, J = 7.5 Hz, 3H, CH₃), 1.19 (t, J = 7.5 Hz, 6H, CH₃), 2.29 (s, 3H, CH₃), 2.35 (s, 3H, CH₃), 2.63 (t, J = 5.0 Hz, 8H, CH₂), 2.80 (q, J = 7.5 Hz, 4H, CH₂), 3.26 (q, J = 7.5 Hz, 2H, CH₂), 3.50 (t, J = 5.0 Hz, 8H, CH₂), 3.77 (s, 4H, CH₂), 4.22 (d, J = 4.0 Hz, 2H, CH₂), 4.60 (br, 1H, NH), 6.17 (s, 1H, ArH), 6.38 (s, 1H, ArH); ¹³C NMR (126 MHz, CDCl₃) δ 15.7, 16.5, 21.2, 21.3, 22.9, 23.8, 40.8, 52.3, 55.2, 59.7, 102.7, 114.1, 131.6, 132.6, 143.5, 145.8, 149.7, 156.2, 158.0; MS (ESI): m/z calculated for C₃₀H₅₁N₄O₄: 531.4 [M + H]⁺, found 531.4; R_f = 0.50 (Al₂O₃, CHCl₃/CH₃OH 7:1). Crystals of the title compound suitable for X-ray analysis were obtained as colourless blocks by diffusion of n-hexane into a solution of the compound in THF.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound hydrogen atoms and protons of the minor (12%) positions of the disordered OH groups (H1A, H2A) were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.95 Å (aromatic) and 0.99 Å (methylene) and U_iso(H) = 1.2 U_eq(C), and O—H = 0.84 Å (OH) and C—H = 0.98 Å (methyl) and U_iso(H) = 1.5 U_eq(C,O), respectively. The protons of the N—H and O—H (undisordered or the main positions) were located from the residual electron density map and refined with U_iso(H) bound to the parent atom (1.2, for NH and 1.5 for OH) with distance restraints for the OH bonds (SADI). The refinement of the disordered N(CH₂CH₂OH)₂ group was performed using geometry (SAME) and U_ij (SIMU, RIGU) restrains implemented in SHELXL (Sheldrick, 2015 ). The refined proportion of the two positions is 88:12%. The maximum residual peak of 0.55 e Å⁻³ is located inside a 27.5 Å³ void and can be refined as a partially occupied water molecule (∼6%); however, due to the low occupancy, it was not included in the final refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₀H₅₀N₄O₄
M_r	530.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.2508 (3), 15.3046 (4), 15.2593 (3)
β (°)	113.3107 (13)
V (Å³)	3056.43 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.13 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII with CCD area detector
No. of measured, independent and observed [I > 2σ(I)] reflections	22458, 6881, 4968
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.144, 1.03
No. of reflections	6881
No. of parameters	431
No. of restraints	290
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.26
Computer programs: APEX2 and SAINT (Bruker, 2008 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 2191249

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022007411/jq2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022007411/jq2019Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022007411/jq2019Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-{[(3-{[Bis(2-hydroxyethyl)amino]methyl}-5-{[(4,6-dimethylpyridin-2-yl)amino]methyl}-2,4,6-triethylphenyl)methyl](2-hydroxyethyl)amino}ethan-1-ol top

Crystal data top

C₃₀H₅₀N₄O₄	F(000) = 1160
M_r = 530.74	D_x = 1.153 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.2508 (3) Å	Cell parameters from 5468 reflections
b = 15.3046 (4) Å	θ = 2.7–28.2°
c = 15.2593 (3) Å	µ = 0.08 mm⁻¹
β = 113.3107 (13)°	T = 100 K
V = 3056.43 (12) Å³	Rod, colourless
Z = 4	0.20 × 0.13 × 0.12 mm

Data collection top

Bruker Kappa APEXII with CCD area detector diffractometer	R_int = 0.031
Radiation source: fine-focus sealed X-Ray tube	θ_max = 27.4°, θ_min = 3.1°
phi and ω scans	h = −18→17
22458 measured reflections	k = −19→12
6881 independent reflections	l = −19→19
4968 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: mixed
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0773P)² + 0.7833P] where P = (F_o² + 2F_c²)/3
6881 reflections	(Δ/σ)_max = 0.001
431 parameters	Δρ_max = 0.55 e Å⁻³
290 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O3	0.06213 (10)	0.37633 (9)	0.20622 (9)	0.0317 (3)
H3	0.0307 (19)	0.4220 (14)	0.1746 (17)	0.066 (8)*
O4	0.14319 (11)	0.36916 (9)	0.41431 (9)	0.0344 (3)
H4	0.133 (2)	0.3843 (18)	0.3569 (14)	0.075 (9)*
N1	0.27113 (11)	0.44288 (9)	−0.07113 (9)	0.0208 (3)
H1N	0.2143 (16)	0.4558 (13)	−0.0622 (13)	0.031 (5)*
N2	0.15327 (11)	0.43433 (8)	−0.22623 (9)	0.0228 (3)
N4	0.27759 (10)	0.34248 (8)	0.32090 (9)	0.0205 (3)
C1	0.35480 (12)	0.49260 (10)	0.09155 (10)	0.0187 (3)
C2	0.31562 (12)	0.57360 (10)	0.10358 (11)	0.0194 (3)
C3	0.30179 (12)	0.59065 (9)	0.18829 (11)	0.0181 (3)
C4	0.32351 (11)	0.52609 (10)	0.25834 (10)	0.0173 (3)
C5	0.35813 (12)	0.44317 (9)	0.24358 (10)	0.0174 (3)
C6	0.37449 (11)	0.42637 (10)	0.16047 (10)	0.0177 (3)
C7	0.36773 (12)	0.47485 (11)	−0.00056 (11)	0.0221 (3)
H7A	0.387939	0.529168	−0.023767	0.027*
H7B	0.421962	0.430698	0.010295	0.027*
C8	0.25215 (12)	0.43984 (9)	−0.16689 (11)	0.0193 (3)
C9	0.12953 (14)	0.42942 (11)	−0.32090 (12)	0.0267 (4)
C10	0.20380 (14)	0.43045 (11)	−0.35800 (12)	0.0275 (4)
H10	0.185041	0.427754	−0.425011	0.033*
C11	0.30622 (14)	0.43547 (11)	−0.29619 (12)	0.0273 (4)
C12	0.33091 (13)	0.43981 (10)	−0.19916 (11)	0.0233 (3)
H12	0.400235	0.442732	−0.155317	0.028*
C13	0.01792 (15)	0.42276 (15)	−0.38339 (14)	0.0410 (5)
H13A	0.009330	0.414806	−0.449864	0.062*
H13B	−0.016851	0.476413	−0.377828	0.062*
H13C	−0.011639	0.372699	−0.363317	0.062*
C14	0.38925 (17)	0.43524 (14)	−0.33408 (15)	0.0413 (5)
H14A	0.396002	0.376396	−0.356233	0.062*
H14B	0.454117	0.452731	−0.283249	0.062*
H14C	0.371554	0.476451	−0.387372	0.062*
C15	0.28910 (15)	0.64292 (11)	0.02668 (12)	0.0301 (4)
H15A	0.232164	0.678992	0.028352	0.036*
H15B	0.265364	0.614087	−0.036485	0.036*
C16	0.37980 (19)	0.70256 (13)	0.03842 (16)	0.0468 (6)
H16A	0.435285	0.667612	0.033810	0.070*
H16B	0.403792	0.731212	0.100914	0.070*
H16C	0.358268	0.746977	−0.011954	0.070*
C17	0.25925 (12)	0.67846 (10)	0.20094 (12)	0.0220 (3)
H17A	0.275654	0.688014	0.269611	0.026*	0.879 (2)
H17B	0.292937	0.725243	0.179147	0.026*	0.879 (2)
H17C	0.295174	0.699548	0.267252	0.026*	0.121 (2)
H17D	0.268160	0.722174	0.157027	0.026*	0.121 (2)
N3	0.14881 (13)	0.68479 (11)	0.14808 (13)	0.0210 (4)	0.879 (2)
C18	0.09000 (15)	0.61856 (13)	0.17436 (13)	0.0257 (4)	0.879 (2)
H18A	0.067231	0.643267	0.222641	0.031*	0.879 (2)
H18B	0.134482	0.567761	0.203334	0.031*	0.879 (2)
C19	−0.0016 (2)	0.5886 (3)	0.0894 (3)	0.0291 (8)	0.879 (2)
H19A	−0.050599	0.637513	0.064946	0.035*	0.879 (2)
H19B	0.019809	0.569992	0.037941	0.035*	0.879 (2)
O1	−0.04980 (13)	0.51746 (9)	0.11566 (11)	0.0291 (4)	0.879 (2)
H1	−0.0746 (19)	0.5386 (16)	0.1552 (16)	0.044*	0.879 (2)
C20	0.11081 (16)	0.77397 (12)	0.14305 (16)	0.0307 (5)	0.879 (2)
H20A	0.035285	0.772108	0.111954	0.037*	0.879 (2)
H20B	0.135047	0.808013	0.100913	0.037*	0.879 (2)
C21	0.1402 (2)	0.82323 (15)	0.2360 (2)	0.0441 (6)	0.879 (2)
H21A	0.215140	0.831891	0.264051	0.053*	0.879 (2)
H21B	0.107765	0.881661	0.222582	0.053*	0.879 (2)
O2	0.11150 (16)	0.78077 (12)	0.30323 (13)	0.0529 (5)	0.879 (2)
H2	0.0511 (16)	0.801 (2)	0.292 (2)	0.088 (12)*	0.879 (2)
N3A	0.1503 (6)	0.6654 (8)	0.1793 (8)	0.028 (3)	0.121 (2)
C18A	0.0841 (8)	0.6365 (8)	0.0834 (7)	0.022 (2)	0.121 (2)
H18C	0.119291	0.590229	0.062551	0.026*	0.121 (2)
H18D	0.071014	0.686176	0.038571	0.026*	0.121 (2)
C19A	−0.0162 (11)	0.6017 (19)	0.0800 (16)	0.025 (4)	0.121 (2)
H19C	−0.061027	0.650470	0.081917	0.030*	0.121 (2)
H19D	−0.051601	0.568134	0.020504	0.030*	0.121 (2)
O1A	0.0064 (10)	0.5463 (9)	0.1615 (10)	0.051 (3)	0.121 (2)
H1A	−0.040111	0.550860	0.181942	0.076*	0.121 (2)
C20A	0.1121 (12)	0.7331 (9)	0.2246 (10)	0.050 (3)	0.121 (2)
H20C	0.152433	0.732286	0.294424	0.060*	0.121 (2)
H20D	0.039976	0.720561	0.213106	0.060*	0.121 (2)
C21A	0.1192 (18)	0.8226 (10)	0.1859 (13)	0.066 (5)	0.121 (2)
H21C	0.106339	0.867512	0.226497	0.079*	0.121 (2)
H21D	0.189389	0.831435	0.189293	0.079*	0.121 (2)
O2A	0.0491 (14)	0.8342 (12)	0.0907 (11)	0.087 (5)	0.121 (2)
H2A	−0.010553	0.825947	0.087201	0.130*	0.121 (2)
C22	0.31398 (13)	0.54528 (10)	0.35242 (11)	0.0229 (3)
H22A	0.299154	0.490307	0.378670	0.027*
H22B	0.256090	0.585763	0.340778	0.027*
C23	0.41152 (14)	0.58586 (11)	0.42515 (11)	0.0261 (4)
H23A	0.469352	0.546753	0.435284	0.039*
H23B	0.404018	0.594612	0.485670	0.039*
H23C	0.423840	0.642269	0.401207	0.039*
C24	0.37421 (12)	0.37309 (10)	0.31879 (11)	0.0205 (3)
H24A	0.410543	0.322946	0.305591	0.025*
H24B	0.417870	0.396841	0.382251	0.025*
C25	0.21403 (13)	0.29319 (11)	0.23560 (11)	0.0246 (4)
H25A	0.182595	0.243188	0.255098	0.029*
H25B	0.258086	0.269381	0.204862	0.029*
C26	0.13072 (13)	0.34762 (11)	0.16397 (12)	0.0265 (4)
H26A	0.160910	0.398788	0.145041	0.032*
H26B	0.093041	0.312534	0.106152	0.032*
C27	0.29400 (14)	0.29730 (11)	0.41001 (12)	0.0264 (4)
H27A	0.344684	0.330023	0.463986	0.032*
H27B	0.322171	0.238398	0.408799	0.032*
C28	0.19565 (15)	0.28872 (12)	0.42530 (13)	0.0320 (4)
H28A	0.150549	0.245962	0.379068	0.038*
H28B	0.211491	0.265817	0.490291	0.038*
C29	0.41588 (13)	0.33905 (10)	0.14462 (12)	0.0246 (4)
H29A	0.389151	0.326780	0.075312	0.029*
H29B	0.391172	0.292370	0.175083	0.029*
C30	0.53240 (14)	0.33718 (12)	0.18528 (13)	0.0336 (4)
H30A	0.555528	0.279991	0.172831	0.050*
H30B	0.559255	0.347470	0.254260	0.050*
H30C	0.557266	0.382886	0.154862	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0266 (7)	0.0379 (7)	0.0313 (7)	0.0018 (6)	0.0122 (6)	0.0082 (6)
O4	0.0409 (8)	0.0418 (8)	0.0244 (7)	0.0039 (6)	0.0170 (6)	0.0003 (6)
N1	0.0216 (7)	0.0258 (7)	0.0169 (7)	−0.0023 (6)	0.0096 (6)	−0.0033 (5)
N2	0.0267 (8)	0.0207 (7)	0.0218 (7)	0.0009 (5)	0.0103 (6)	0.0008 (5)
N4	0.0258 (7)	0.0192 (6)	0.0153 (6)	−0.0026 (5)	0.0068 (6)	0.0014 (5)
C1	0.0180 (7)	0.0219 (7)	0.0168 (7)	−0.0045 (6)	0.0077 (6)	−0.0025 (6)
C2	0.0188 (8)	0.0188 (7)	0.0194 (8)	−0.0033 (6)	0.0063 (6)	0.0013 (6)
C3	0.0167 (7)	0.0153 (7)	0.0221 (8)	−0.0014 (6)	0.0075 (6)	−0.0011 (6)
C4	0.0169 (7)	0.0172 (7)	0.0188 (7)	−0.0023 (6)	0.0084 (6)	−0.0027 (6)
C5	0.0178 (7)	0.0169 (7)	0.0168 (7)	−0.0005 (6)	0.0062 (6)	0.0000 (6)
C6	0.0167 (7)	0.0182 (7)	0.0183 (7)	−0.0008 (6)	0.0069 (6)	−0.0036 (6)
C7	0.0215 (8)	0.0286 (8)	0.0180 (8)	−0.0041 (7)	0.0096 (7)	−0.0028 (6)
C8	0.0261 (8)	0.0147 (7)	0.0185 (7)	0.0000 (6)	0.0104 (7)	0.0001 (6)
C9	0.0325 (10)	0.0221 (8)	0.0232 (8)	−0.0002 (7)	0.0088 (7)	−0.0002 (6)
C10	0.0395 (10)	0.0268 (9)	0.0174 (8)	−0.0027 (7)	0.0127 (8)	−0.0005 (6)
C11	0.0360 (10)	0.0255 (8)	0.0261 (9)	−0.0049 (7)	0.0184 (8)	−0.0036 (7)
C12	0.0246 (9)	0.0254 (8)	0.0210 (8)	−0.0029 (7)	0.0101 (7)	−0.0038 (6)
C13	0.0350 (11)	0.0513 (12)	0.0294 (10)	0.0004 (9)	0.0047 (9)	0.0011 (9)
C14	0.0483 (13)	0.0514 (12)	0.0367 (11)	−0.0127 (10)	0.0301 (10)	−0.0116 (9)
C15	0.0458 (11)	0.0221 (8)	0.0234 (8)	−0.0009 (8)	0.0145 (8)	0.0052 (7)
C16	0.0773 (17)	0.0288 (10)	0.0509 (13)	−0.0146 (10)	0.0429 (13)	−0.0012 (9)
C17	0.0218 (8)	0.0189 (7)	0.0255 (8)	0.0010 (6)	0.0093 (7)	−0.0014 (6)
N3	0.0214 (9)	0.0169 (8)	0.0247 (9)	0.0047 (6)	0.0092 (7)	0.0066 (7)
C18	0.0249 (10)	0.0268 (10)	0.0260 (10)	0.0008 (8)	0.0109 (8)	0.0009 (8)
C19	0.0286 (13)	0.0305 (17)	0.0260 (13)	0.0004 (12)	0.0085 (10)	0.0001 (10)
O1	0.0237 (8)	0.0311 (8)	0.0342 (8)	0.0008 (6)	0.0130 (7)	−0.0026 (6)
C20	0.0276 (11)	0.0183 (9)	0.0487 (13)	0.0081 (8)	0.0178 (10)	0.0071 (9)
C21	0.0336 (14)	0.0276 (11)	0.0711 (18)	0.0065 (10)	0.0207 (14)	−0.0135 (12)
O2	0.0628 (13)	0.0487 (10)	0.0471 (10)	0.0246 (9)	0.0218 (10)	−0.0080 (8)
N3A	0.025 (5)	0.018 (5)	0.035 (5)	−0.001 (4)	0.006 (4)	−0.002 (4)
C18A	0.013 (4)	0.020 (5)	0.027 (5)	0.003 (4)	0.002 (4)	−0.004 (4)
C19A	0.019 (6)	0.021 (7)	0.033 (7)	−0.005 (5)	0.008 (5)	−0.014 (5)
O1A	0.026 (6)	0.069 (8)	0.053 (7)	0.011 (6)	0.011 (5)	0.021 (6)
C20A	0.046 (6)	0.042 (5)	0.054 (6)	0.008 (5)	0.010 (5)	−0.012 (5)
C21A	0.060 (8)	0.047 (7)	0.077 (8)	0.007 (6)	0.013 (7)	0.004 (6)
O2A	0.077 (10)	0.096 (11)	0.080 (8)	0.027 (8)	0.023 (7)	0.017 (7)
C22	0.0326 (9)	0.0182 (7)	0.0236 (8)	−0.0005 (7)	0.0174 (7)	−0.0018 (6)
C23	0.0374 (10)	0.0228 (8)	0.0195 (8)	0.0007 (7)	0.0126 (7)	−0.0035 (6)
C24	0.0243 (8)	0.0183 (7)	0.0173 (7)	0.0015 (6)	0.0066 (7)	0.0012 (6)
C25	0.0284 (9)	0.0214 (8)	0.0227 (8)	−0.0037 (7)	0.0088 (7)	−0.0026 (6)
C26	0.0259 (9)	0.0329 (9)	0.0197 (8)	−0.0065 (7)	0.0077 (7)	−0.0001 (7)
C27	0.0341 (10)	0.0245 (8)	0.0195 (8)	−0.0002 (7)	0.0094 (7)	0.0060 (6)
C28	0.0398 (11)	0.0338 (10)	0.0249 (9)	−0.0032 (8)	0.0153 (8)	0.0042 (7)
C29	0.0306 (9)	0.0212 (8)	0.0230 (8)	0.0032 (7)	0.0118 (7)	−0.0040 (6)
C30	0.0323 (10)	0.0331 (9)	0.0348 (10)	0.0130 (8)	0.0128 (8)	−0.0021 (8)

Geometric parameters (Å, º) top

O3—C26	1.436 (2)	C18—C19	1.502 (4)
O3—H3	0.867 (16)	C18—H18A	0.9900
O4—C28	1.415 (2)	C18—H18B	0.9900
O4—H4	0.863 (16)	C19—O1	1.427 (3)
N1—C8	1.3775 (19)	C19—H19A	0.9900
N1—C7	1.456 (2)	C19—H19B	0.9900
N1—H1N	0.89 (2)	O1—H1	0.873 (16)
N2—C8	1.343 (2)	C20—C21	1.512 (3)
N2—C9	1.349 (2)	C20—H20A	0.9900
N4—C27	1.4595 (19)	C20—H20B	0.9900
N4—C25	1.466 (2)	C21—O2	1.404 (3)
N4—C24	1.467 (2)	C21—H21A	0.9900
C1—C2	1.401 (2)	C21—H21B	0.9900
C1—C6	1.407 (2)	O2—H2	0.865 (17)
C1—C7	1.513 (2)	N3A—C18A	1.461 (9)
C2—C3	1.407 (2)	N3A—C20A	1.466 (9)
C2—C15	1.515 (2)	C18A—C19A	1.507 (10)
C3—C4	1.397 (2)	C18A—H18C	0.9900
C3—C17	1.518 (2)	C18A—H18D	0.9900
C4—C5	1.412 (2)	C19A—O1A	1.433 (10)
C4—C22	1.523 (2)	C19A—H19C	0.9900
C5—C6	1.4010 (19)	C19A—H19D	0.9900
C5—C24	1.521 (2)	O1A—H1A	0.8400
C6—C29	1.518 (2)	C20A—C21A	1.511 (10)
C7—H7A	0.9900	C20A—H20C	0.9900
C7—H7B	0.9900	C20A—H20D	0.9900
C8—C12	1.393 (2)	C21A—O2A	1.411 (10)
C9—C10	1.384 (2)	C21A—H21C	0.9900
C9—C13	1.500 (3)	C21A—H21D	0.9900
C10—C11	1.392 (3)	O2A—H2A	0.8400
C10—H10	0.9500	C22—C23	1.526 (2)
C11—C12	1.381 (2)	C22—H22A	0.9900
C11—C14	1.509 (2)	C22—H22B	0.9900
C12—H12	0.9500	C23—H23A	0.9800
C13—H13A	0.9800	C23—H23B	0.9800
C13—H13B	0.9800	C23—H23C	0.9800
C13—H13C	0.9800	C24—H24A	0.9900
C14—H14A	0.9800	C24—H24B	0.9900
C14—H14B	0.9800	C25—C26	1.507 (2)
C14—H14C	0.9800	C25—H25A	0.9900
C15—C16	1.534 (3)	C25—H25B	0.9900
C15—H15A	0.9900	C26—H26A	0.9900
C15—H15B	0.9900	C26—H26B	0.9900
C16—H16A	0.9800	C27—C28	1.515 (2)
C16—H16B	0.9800	C27—H27A	0.9900
C16—H16C	0.9800	C27—H27B	0.9900
C17—N3	1.460 (2)	C28—H28A	0.9900
C17—N3A	1.468 (8)	C28—H28B	0.9900
C17—H17A	0.9900	C29—C30	1.526 (2)
C17—H17B	0.9900	C29—H29A	0.9900
C17—H17C	0.9900	C29—H29B	0.9900
C17—H17D	0.9900	C30—H30A	0.9800
N3—C20	1.459 (2)	C30—H30B	0.9800
N3—C18	1.469 (2)	C30—H30C	0.9800

C26—O3—H3	106.9 (18)	H19A—C19—H19B	108.2
C28—O4—H4	102.7 (19)	C19—O1—H1	106.4 (17)
C8—N1—C7	121.81 (13)	N3—C20—C21	117.25 (18)
C8—N1—H1N	111.1 (12)	N3—C20—H20A	108.0
C7—N1—H1N	117.4 (12)	C21—C20—H20A	108.0
C8—N2—C9	118.51 (14)	N3—C20—H20B	108.0
C27—N4—C25	113.46 (12)	C21—C20—H20B	108.0
C27—N4—C24	111.47 (13)	H20A—C20—H20B	107.2
C25—N4—C24	113.60 (12)	O2—C21—C20	113.70 (19)
C2—C1—C6	120.77 (13)	O2—C21—H21A	108.8
C2—C1—C7	118.81 (13)	C20—C21—H21A	108.8
C6—C1—C7	120.24 (13)	O2—C21—H21B	108.8
C1—C2—C3	119.50 (13)	C20—C21—H21B	108.8
C1—C2—C15	120.56 (13)	H21A—C21—H21B	107.7
C3—C2—C15	119.94 (14)	C21—O2—H2	104 (2)
C4—C3—C2	120.16 (13)	C18A—N3A—C20A	118.3 (9)
C4—C3—C17	120.50 (13)	C18A—N3A—C17	118.2 (8)
C2—C3—C17	119.29 (13)	C20A—N3A—C17	110.8 (8)
C3—C4—C5	119.95 (13)	N3A—C18A—C19A	111.7 (11)
C3—C4—C22	120.61 (13)	N3A—C18A—H18C	109.3
C5—C4—C22	119.40 (13)	C19A—C18A—H18C	109.3
C6—C5—C4	120.22 (13)	N3A—C18A—H18D	109.3
C6—C5—C24	121.63 (13)	C19A—C18A—H18D	109.3
C4—C5—C24	118.13 (12)	H18C—C18A—H18D	107.9
C5—C6—C1	119.28 (13)	O1A—C19A—C18A	107.1 (10)
C5—C6—C29	121.33 (13)	O1A—C19A—H19C	110.3
C1—C6—C29	119.37 (12)	C18A—C19A—H19C	110.3
N1—C7—C1	108.68 (12)	O1A—C19A—H19D	110.3
N1—C7—H7A	110.0	C18A—C19A—H19D	110.3
C1—C7—H7A	110.0	H19C—C19A—H19D	108.5
N1—C7—H7B	110.0	C19A—O1A—H1A	109.5
C1—C7—H7B	110.0	N3A—C20A—C21A	111.2 (12)
H7A—C7—H7B	108.3	N3A—C20A—H20C	109.4
N2—C8—N1	115.51 (13)	C21A—C20A—H20C	109.4
N2—C8—C12	122.62 (14)	N3A—C20A—H20D	109.4
N1—C8—C12	121.84 (15)	C21A—C20A—H20D	109.4
N2—C9—C10	121.94 (16)	H20C—C20A—H20D	108.0
N2—C9—C13	115.99 (15)	O2A—C21A—C20A	112.8 (12)
C10—C9—C13	122.07 (16)	O2A—C21A—H21C	109.0
C9—C10—C11	119.35 (15)	C20A—C21A—H21C	109.0
C9—C10—H10	120.3	O2A—C21A—H21D	109.0
C11—C10—H10	120.3	C20A—C21A—H21D	109.0
C12—C11—C10	118.89 (15)	H21C—C21A—H21D	107.8
C12—C11—C14	120.34 (17)	C21A—O2A—H2A	109.5
C10—C11—C14	120.76 (15)	C4—C22—C23	111.64 (13)
C11—C12—C8	118.68 (16)	C4—C22—H22A	109.3
C11—C12—H12	120.7	C23—C22—H22A	109.3
C8—C12—H12	120.7	C4—C22—H22B	109.3
C9—C13—H13A	109.5	C23—C22—H22B	109.3
C9—C13—H13B	109.5	H22A—C22—H22B	108.0
H13A—C13—H13B	109.5	C22—C23—H23A	109.5
C9—C13—H13C	109.5	C22—C23—H23B	109.5
H13A—C13—H13C	109.5	H23A—C23—H23B	109.5
H13B—C13—H13C	109.5	C22—C23—H23C	109.5
C11—C14—H14A	109.5	H23A—C23—H23C	109.5
C11—C14—H14B	109.5	H23B—C23—H23C	109.5
H14A—C14—H14B	109.5	N4—C24—C5	112.30 (13)
C11—C14—H14C	109.5	N4—C24—H24A	109.1
H14A—C14—H14C	109.5	C5—C24—H24A	109.1
H14B—C14—H14C	109.5	N4—C24—H24B	109.1
C2—C15—C16	112.70 (16)	C5—C24—H24B	109.1
C2—C15—H15A	109.1	H24A—C24—H24B	107.9
C16—C15—H15A	109.1	N4—C25—C26	113.08 (14)
C2—C15—H15B	109.1	N4—C25—H25A	109.0
C16—C15—H15B	109.1	C26—C25—H25A	109.0
H15A—C15—H15B	107.8	N4—C25—H25B	109.0
C15—C16—H16A	109.5	C26—C25—H25B	109.0
C15—C16—H16B	109.5	H25A—C25—H25B	107.8
H16A—C16—H16B	109.5	O3—C26—C25	108.92 (13)
C15—C16—H16C	109.5	O3—C26—H26A	109.9
H16A—C16—H16C	109.5	C25—C26—H26A	109.9
H16B—C16—H16C	109.5	O3—C26—H26B	109.9
N3—C17—C3	112.70 (14)	C25—C26—H26B	109.9
N3A—C17—C3	106.9 (5)	H26A—C26—H26B	108.3
N3—C17—H17A	109.1	N4—C27—C28	111.58 (14)
C3—C17—H17A	109.1	N4—C27—H27A	109.3
N3—C17—H17B	109.1	C28—C27—H27A	109.3
C3—C17—H17B	109.1	N4—C27—H27B	109.3
H17A—C17—H17B	107.8	C28—C27—H27B	109.3
N3A—C17—H17C	110.3	H27A—C27—H27B	108.0
C3—C17—H17C	110.3	O4—C28—C27	112.57 (14)
N3A—C17—H17D	110.3	O4—C28—H28A	109.1
C3—C17—H17D	110.3	C27—C28—H28A	109.1
H17C—C17—H17D	108.6	O4—C28—H28B	109.1
C20—N3—C17	112.80 (16)	C27—C28—H28B	109.1
C20—N3—C18	114.82 (16)	H28A—C28—H28B	107.8
C17—N3—C18	114.22 (15)	C6—C29—C30	112.38 (14)
N3—C18—C19	111.71 (17)	C6—C29—H29A	109.1
N3—C18—H18A	109.3	C30—C29—H29A	109.1
C19—C18—H18A	109.3	C6—C29—H29B	109.1
N3—C18—H18B	109.3	C30—C29—H29B	109.1
C19—C18—H18B	109.3	H29A—C29—H29B	107.9
H18A—C18—H18B	107.9	C29—C30—H30A	109.5
O1—C19—C18	109.9 (2)	C29—C30—H30B	109.5
O1—C19—H19A	109.7	H30A—C30—H30B	109.5
C18—C19—H19A	109.7	C29—C30—H30C	109.5
O1—C19—H19B	109.7	H30A—C30—H30C	109.5
C18—C19—H19B	109.7	H30B—C30—H30C	109.5

C6—C1—C2—C3	3.9 (2)	N2—C8—C12—C11	1.1 (2)
C7—C1—C2—C3	179.11 (14)	N1—C8—C12—C11	179.13 (15)
C6—C1—C2—C15	−176.63 (15)	C1—C2—C15—C16	−88.89 (19)
C7—C1—C2—C15	−1.5 (2)	C3—C2—C15—C16	90.55 (19)
C1—C2—C3—C4	−2.3 (2)	C4—C3—C17—N3	−99.98 (17)
C15—C2—C3—C4	178.26 (15)	C2—C3—C17—N3	77.67 (18)
C1—C2—C3—C17	−179.95 (14)	C4—C3—C17—N3A	−77.6 (6)
C15—C2—C3—C17	0.6 (2)	C2—C3—C17—N3A	100.1 (6)
C2—C3—C4—C5	−0.8 (2)	C3—C17—N3—C20	−167.61 (15)
C17—C3—C4—C5	176.79 (14)	C3—C17—N3—C18	58.88 (19)
C2—C3—C4—C22	176.88 (14)	C20—N3—C18—C19	83.7 (3)
C17—C3—C4—C22	−5.5 (2)	C17—N3—C18—C19	−143.8 (2)
C3—C4—C5—C6	2.4 (2)	N3—C18—C19—O1	173.3 (2)
C22—C4—C5—C6	−175.35 (14)	C17—N3—C20—C21	−52.4 (2)
C3—C4—C5—C24	−176.09 (14)	C18—N3—C20—C21	80.8 (2)
C22—C4—C5—C24	6.2 (2)	N3—C20—C21—O2	−56.8 (3)
C4—C5—C6—C1	−0.8 (2)	C3—C17—N3A—C18A	−61.6 (11)
C24—C5—C6—C1	177.64 (14)	C3—C17—N3A—C20A	157.2 (8)
C4—C5—C6—C29	177.43 (14)	C20A—N3A—C18A—C19A	−58.0 (19)
C24—C5—C6—C29	−4.1 (2)	C17—N3A—C18A—C19A	163.7 (14)
C2—C1—C6—C5	−2.4 (2)	N3A—C18A—C19A—O1A	−45 (3)
C7—C1—C6—C5	−177.49 (14)	C18A—N3A—C20A—C21A	−77.9 (15)
C2—C1—C6—C29	179.35 (14)	C17—N3A—C20A—C21A	63.2 (15)
C7—C1—C6—C29	4.2 (2)	N3A—C20A—C21A—O2A	70 (2)
C8—N1—C7—C1	165.06 (14)	C3—C4—C22—C23	−85.93 (18)
C2—C1—C7—N1	−85.21 (17)	C5—C4—C22—C23	91.81 (17)
C6—C1—C7—N1	90.00 (17)	C27—N4—C24—C5	−162.08 (12)
C9—N2—C8—N1	−178.75 (14)	C25—N4—C24—C5	68.22 (16)
C9—N2—C8—C12	−0.6 (2)	C6—C5—C24—N4	−108.97 (16)
C7—N1—C8—N2	−161.06 (14)	C4—C5—C24—N4	69.50 (18)
C7—N1—C8—C12	20.8 (2)	C27—N4—C25—C26	132.61 (15)
C8—N2—C9—C10	−0.4 (2)	C24—N4—C25—C26	−98.70 (15)
C8—N2—C9—C13	179.58 (15)	N4—C25—C26—O3	−63.25 (17)
N2—C9—C10—C11	0.9 (2)	C25—N4—C27—C28	−66.62 (18)
C13—C9—C10—C11	−179.07 (17)	C24—N4—C27—C28	163.61 (13)
C9—C10—C11—C12	−0.4 (2)	N4—C27—C28—O4	−50.53 (19)
C9—C10—C11—C14	179.00 (16)	C5—C6—C29—C30	−88.66 (18)
C10—C11—C12—C8	−0.6 (2)	C1—C6—C29—C30	89.57 (18)
C14—C11—C12—C8	−179.97 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O4ⁱ	0.84	1.99	2.763 (18)	152
O1A—H1A···N2ⁱⁱ	0.84	1.99	2.832 (12)	178
C18A—H18D···O2A	0.99	2.46	3.08 (2)	120
O2—H2···O3ⁱ	0.87 (2)	1.99 (2)	2.828 (2)	162 (3)
O1—H1···N2ⁱⁱ	0.87 (2)	1.89 (2)	2.7449 (19)	167 (3)
N1—H1N···O1ⁱⁱ	0.89 (2)	2.19 (2)	3.014 (2)	152.0 (17)
C22—H22A···N4	0.99	2.40	3.152 (2)	132
C18—H18A···O2	0.99	2.39	3.106 (3)	128
C15—H15A···N3	0.99	2.54	3.282 (3)	131
C13—H13A···O2Aⁱⁱⁱ	0.98	2.33	3.220 (14)	151
C10—H10···O4^iv	0.95	2.45	3.365 (2)	161
O4—H4···O3	0.86 (2)	2.12 (2)	2.9200 (18)	155 (3)
O3—H3···O1A	0.87 (2)	1.93 (2)	2.727 (13)	152 (3)
O3—H3···O1	0.87 (2)	1.86 (2)	2.7156 (19)	172 (3)

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

Funding information

Open access funding by the Publication Fund of the Technische Universität Bergakademie Freiberg is gratefully acknowledged.

References

Amrhein, F., Lippe, J. & Mazik, M. (2016). Org. Biomol. Chem. 14, 10648–10659. Web of Science CrossRef CAS PubMed Google Scholar
Amrhein, F. & Mazik, M. (2021). Eur. J. Org. Chem. pp. 6282–6303. Web of Science CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond In Structural Chemistry and Biology, IUCr Monographs on Crystallography, Vol. 9. New York: Oxford University Press. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Geffert, C., Kuschel, M. & Mazik, M. (2013). J. Org. Chem. 78, 292–300. CrossRef CAS PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hennrich, G. & Anslyn, E. V. (2002). Chem. Eur. J. 8, 2218–2224. CrossRef PubMed CAS Google Scholar
Kaiser, S., Geffert, C. & Mazik, M. (2019). Eur. J. Org. Chem. pp. 7555–7562. Web of Science CrossRef Google Scholar
Koch, N., Seichter, W. & Mazik, M. (2016). Synthesis, 48, 2757–2767. CAS Google Scholar
Köhler, L., Hübler, C., Seichter, W. & Mazik, M. (2021). RSC Adv. 11, 22221–22229. Web of Science PubMed Google Scholar
Köhler, L., Seichter, W. & Mazik, M. (2020). Eur. J. Org. Chem. pp. 7023–7034. Google Scholar
Lippe, J. & Mazik, M. (2015). J. Org. Chem. 80, 1427–1439. Web of Science CrossRef CAS PubMed Google Scholar
Lippe, J., Seichter, W. & Mazik, M. (2015). Org. Biomol. Chem. 13, 11622–11632. CSD CrossRef CAS PubMed Google Scholar
Mazik, M. (2009). Chem. Soc. Rev. 38, 935–956. Web of Science CrossRef PubMed CAS Google Scholar
Mazik, M. (2012). RSC Adv. 2, 2630–2642. Web of Science CrossRef CAS Google Scholar
Mazik, M. & Hartmann, A. (2008). J. Org. Chem. 73, 7444–7450. Web of Science CSD CrossRef PubMed CAS Google Scholar
Mazik, M., Hartmann, A. & Jones, P. G. (2009). Chem. Eur. J. 15, 9147–9159. Web of Science CSD CrossRef PubMed CAS Google Scholar
Mazik, M., Radunz, W. & Boese, R. (2004). J. Org. Chem. 69, 7448–7462. Web of Science CSD CrossRef PubMed CAS Google Scholar
Nishio, M., Umezawa, Y., Hirota, M. & Takeuchi, Y. (1995). Tetrahedron, 51, 8665–8701. CrossRef CAS Web of Science Google Scholar
Quiocho, F. A. (1989). Pure Appl. Chem. 61, 1293–1306. CrossRef CAS Web of Science Google Scholar
Rosien, J.-R., Seichter, W. & Mazik, M. (2013). Org. Biomol. Chem. 11, 6569–6579. CSD CrossRef CAS PubMed Google Scholar
Schulze, M. M., Koch, N., Seichter, W. & Mazik, M. (2018). Eur. J. Org. Chem. pp. 4317–4330. CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2015). Acta Cryst. C71, 9–18. Web of Science CrossRef IUCr Journals Google Scholar
Stapf, M., Seichter, W. & Mazik, M. (2015). Chem. Eur. J. 21, 6350–6354. Web of Science CSD CrossRef CAS PubMed Google Scholar
Stapf, M., Seichter, W. & Mazik, M. (2020a). Acta Cryst. E76, 1679–1683. CSD CrossRef IUCr Journals Google Scholar
Stapf, M., Seichter, W. & Mazik, M. (2020b). Eur. J. Org. Chem. pp. 4900–4915. CSD CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.