(2-Hy­droxy­phen­yl)(4,2′:4′,4′′-terpyridin-6′-yl)methanone

Devika, S.; Begum, N.S.; Manjappa, K.B.; Yang, D.-Y.

doi:10.1107/S2414314620008573

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 7| July 2020| x200857

https://doi.org/10.1107/S2414314620008573

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(2-Hydroxyphenyl)(4,2′:4′,4′′-terpyridin-6′-yl)methanone

S. Devika,^a Noor Shahina Begum,^a ^* Kiran B. Manjappa ^b ^* and Ding-Yah Yang ^b

^aDepartment of Chemistry, Bangalore University, Jnana Bharathi Campus, Bangalore-560 056, Karnataka, India, and ^bGraduate Program for Biomedical and Materials Science, Department of Chemistry, Tunghai University, No. 1727, Sec. 4, Taiwan Boulevard, Xitun District, Taichung-40704, Taiwan
^*Correspondence e-mail: noorsb05@gmail.com, kiran@thu.edu.tw

Edited by O. Blacque, University of Zürich, Switzerland (Received 27 May 2020; accepted 25 June 2020; online 10 July 2020)

The title compound, C₂₂H₁₅N₃O₂, can be described as a ketone with a phenol substituent and a terpyridine ligand coordinated to the carbonyl group. The three six-membered rings of the terpyridine ligand are not coplanar. The dihedral angles between the mean planes of the central ring and the external pyridine ligands are 22.77 (9) and 26.77 (7)°. The central ring of the terpyridine ligand is also not coplanar with the o-hydroxy phenyl ring, the dihedral angle being 39.72 (5)°. An intramolecular O—H⋯O hydrogen bond occurs. The crystal structure of the title compound is consolidated by C—H⋯O and C—H⋯N hydrogen bonding interactions.

Keywords: crystal structure; terpyridine; ketone; crystal structure.

CCDC reference: 2012289

Structure description

Pyridine and derivatives play critical roles in the biochemical field. The hydrazone derivatives of benzoylpyridines exhibit cytotoxic activity towards tumor cell lines (Santos et al., 2018 ) and show excellent antiproliferative activity (Kalinowski et al., 2007 ). The quest for an efficient method for the preparation of such pyridine derivatives is ongoing. Herein, we report a novel method for the preparation of a 2-benzoylpyridine derivative in a one-pot reaction of 3-aminocoumarin with 4-acetylpyridine. The structural elucidation of the compound by spectroscopic investigation and single-crystal analysis has been performed.

The molecular structure of the title compound is shown in Fig. 1. It crystallizes in the orthorhombic crystal system in P2₁2₁2₁ space group with one molecule in the asymmetric unit. The compound can be described as a ketone with a phenol substituent and a terpyridine ligand coordinated to the carbonyl group. The dihedral angle between the mean planes of the central ring of the terpyridine ligand and the o-hydroxy phenyl ring is 39.72 (5)°. The three six-membered rings of the terpyridine ligand are not coplanar. The dihedral angles between the mean planes of the central ring and the external pyridine ligands are 22.77 (9) and 26.77 (7)° (for C13–C17/N2 and C18–C22/N3, respectively). A strong intramolecular O—H⋯O hydrogen bond (O2—H2′⋯O1) exists between the O1 and O2 atoms of the phenol ring (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2′⋯O1	0.87 (4)	1.73 (4)	2.527 (3)	152 (3)
C16—H16⋯O2ⁱ	0.95	2.59	3.309 (3)	132
C17—H17⋯N2ⁱⁱ	0.95	2.49	3.344 (3)	150
C21—H21⋯O1ⁱⁱⁱ	0.95	2.45	3.380 (3)	165
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y-1, z.

Figure 1
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

The crystal packing features the C21—H21⋯O1 interaction along the crystallographic a axis. The O1 atom of the phenol group is involves in both intra- and inter-molecular hydrogen bonding (Table 1, Fig. 2). The crystal structure is further stabilized by the following intermolecular interactions: C17—H17⋯N2ⁱⁱ [symmetry code: (ii) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ], which connects the molecules in a zigzag pattern, and C16—H16⋯O2ⁱ [symmetry code: (i) −x + $[{3\over 2}]$ , −y + 1, z − $[{1\over 2}]$ ], which forms molecular chains along the crystallographic b and a axes, respectively (Fig. 3). In addition, a weak π–π stacking interaction exhibiting a centroid–centroid distance of 3.7919 (15) Å between C7–C12 and C13–C17/N2 rings is observed (Fig. 4).

Figure 2
Unit-cell packing of the title compound showing intramolecular O—H⋯O and intermolecular C—H⋯O interactions as dotted lines. H atoms not involved in hydrogen bonding have been excluded.

Figure 3
Unit-cell packing of the title compound showing intermolecular C—H⋯N and C—H⋯O interactions as dotted lines. H atoms not involved in hydrogen bonding have been excluded.

Figure 4
Unit-cell packing depicting the intermolecular π–π stacking interactions as dotted lines.

Synthesis and crystallization

A mixture of 3-amino-4-hydroxycoumarin (10 mmol, 1.0 equiv.), 4-acetylpyridine (22 mmol, 2.2 equiv.) and a few drops of TEA (0.2 equiv.) in toluene (25 ml) was refluxed under nitrogen for 4 h. The progress of the reaction was monitored by TLC. The reaction mixture was allowed to attain room temperature and the solvent was dried using a rotary evaporator. The crude product was purified by flash column chromatography to obtain a yellowish brown solid with 67% yield, R_f = 0.10 (5% DCM/MeOH), m.p. 190–192°C. The compound was recrystallized from ethanol solution. ¹H NMR (CDCl₃, 400 MHz) δ 12.13 (s, 1H), 8.84 (d, J = 6.4 Hz, 2H), 8.81 (d, J = 6.4 Hz, 2H), 8.25 (dd, J = 8.0, 1.2 Hz, 1H), 8.22 (d, J = 1.2 Hz, 1H), 8.19 (d, J = 1.2 Hz, 1H), 8.01 (dd, J = 4.8, 1.6 Hz, 2H), 7.66 (dd, J = 3.2, 1.6 Hz, 2H), 7.58 (t, J = 7.6 Hz, 1H), 7.12 (d, J = 8.4–0 Hz, 1H), 6.96 (t, J = 7.2 Hz, 1H); ¹³C NMR (CDCl₃, 150 MHz) δ 196.7, 164.9, 156.6, 154.4, 150.9, 150.8, 150.7, 148.7, 144.8, 144.6, 137.1, 134.2, 122.3, 121.4, 121.1, 120.4, 118.9, 118.5.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₁₅N₃O₂
M_r	353.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	7.2994 (2), 9.6105 (3), 23.9296 (8)
V (Å³)	1678.68 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.25 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998 )
T_min, T_max	0.879, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	23873, 3416, 3003
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.088, 1.10
No. of reflections	3416
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23
Computer programs: SMART and SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 2012289

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314620008573/zq4040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620008573/zq4040Isup2.hkl

Reaction Scheme. DOI: https://doi.org/10.1107/S2414314620008573/zq4040sup3.png

Proton-NMR. DOI: https://doi.org/10.1107/S2414314620008573/zq4040sup4.pdf

13C-NMR. DOI: https://doi.org/10.1107/S2414314620008573/zq4040sup5.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2414314620008573/zq4040Isup6.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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: SHELXL2018/3 (Sheldrick, 2015).

(2-Hydroxyphenyl)(4,2':4',4''-terpyridin-6'-yl)methanone top

Crystal data top

C₂₂H₁₅N₃O₂	D_x = 1.398 Mg m⁻³
M_r = 353.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9903 reflections
a = 7.2994 (2) Å	θ = 2.9–26.3°
b = 9.6105 (3) Å	µ = 0.09 mm⁻¹
c = 23.9296 (8) Å	T = 150 K
V = 1678.68 (9) Å³	Parallelepiped, yellow
Z = 4	0.48 × 0.25 × 0.18 mm
F(000) = 736

Data collection top

Bruker SMART APEX CCD diffractometer	3003 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
ω scans	θ_max = 26.4°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→8
T_min = 0.879, T_max = 0.928	k = −12→11
23873 measured reflections	l = −29→29
3416 independent reflections

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)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0377P)² + 0.4435P] where P = (F_o² + 2F_c²)/3
3416 reflections	(Δ/σ)_max = 0.001
248 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.23 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 hydroxy H atom was located in the Fourier maps and freyly refined, while all other H atoms were fixed geometrically and allow to ride on their parent carbon atoms, with a C—H distance of 0.95 Å and U_iso(H) = 1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq
O1	0.6864 (3)	0.49905 (18)	1.05784 (7)	0.0296 (4)
O2	0.7035 (3)	0.49051 (18)	1.16325 (7)	0.0321 (4)
H2'	0.706 (5)	0.522 (3)	1.1292 (14)	0.051 (10)*
N1	0.6398 (3)	0.18406 (19)	0.98997 (7)	0.0195 (4)
N2	0.3663 (3)	0.6191 (2)	0.76383 (9)	0.0348 (6)
N3	0.8135 (4)	−0.2862 (2)	0.91678 (9)	0.0367 (6)
C1	0.6004 (3)	0.3190 (2)	0.99800 (9)	0.0193 (5)
C2	0.5477 (3)	0.4093 (2)	0.95579 (9)	0.0201 (5)
H2	0.525464	0.504644	0.963740	0.024*
C3	0.5278 (3)	0.3587 (2)	0.90164 (9)	0.0197 (5)
C4	0.5690 (3)	0.2187 (2)	0.89279 (9)	0.0199 (5)
H4	0.557492	0.179870	0.856446	0.024*
C5	0.6269 (3)	0.1354 (2)	0.93715 (9)	0.0194 (5)
C6	0.6289 (3)	0.3781 (2)	1.05576 (9)	0.0211 (5)
C7	0.5894 (3)	0.2996 (2)	1.10698 (9)	0.0195 (5)
C8	0.5071 (3)	0.1676 (2)	1.10724 (10)	0.0220 (5)
H8	0.476367	0.124708	1.072717	0.026*
C9	0.4699 (3)	0.0988 (3)	1.15652 (10)	0.0263 (5)
H9	0.414255	0.009436	1.155914	0.032*
C10	0.5147 (4)	0.1617 (3)	1.20729 (10)	0.0296 (6)
H10	0.490145	0.114222	1.241306	0.036*
C11	0.5937 (4)	0.2912 (3)	1.20868 (10)	0.0294 (6)
H11	0.623645	0.332654	1.243546	0.035*
C12	0.6301 (3)	0.3618 (2)	1.15932 (10)	0.0230 (5)
C13	0.4716 (3)	0.4501 (2)	0.85454 (9)	0.0208 (5)
C14	0.3732 (4)	0.5721 (3)	0.86268 (10)	0.0281 (6)
H14	0.339665	0.600640	0.899286	0.034*
C15	0.3244 (4)	0.6518 (3)	0.81667 (11)	0.0350 (6)
H15	0.256962	0.734852	0.823080	0.042*
C16	0.4630 (4)	0.5027 (3)	0.75683 (11)	0.0315 (6)
H16	0.496579	0.477605	0.719817	0.038*
C17	0.5177 (3)	0.4161 (3)	0.79977 (10)	0.0248 (5)
H17	0.586121	0.334272	0.792006	0.030*
C18	0.6840 (3)	−0.0113 (2)	0.92905 (9)	0.0205 (5)
C19	0.7538 (3)	−0.0593 (3)	0.87856 (10)	0.0252 (5)
H19	0.759270	0.000724	0.847051	0.030*
C20	0.8152 (4)	−0.1948 (3)	0.87460 (11)	0.0333 (6)
H20	0.861862	−0.225112	0.839599	0.040*
C21	0.7440 (4)	−0.2392 (3)	0.96517 (11)	0.0321 (6)
H21	0.739621	−0.301578	0.995929	0.039*
C22	0.6785 (4)	−0.1058 (2)	0.97307 (10)	0.0250 (5)
H22	0.630106	−0.078786	1.008290	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0424 (11)	0.0236 (9)	0.0228 (9)	−0.0076 (8)	−0.0032 (8)	0.0015 (7)
O2	0.0489 (12)	0.0263 (10)	0.0212 (9)	−0.0064 (8)	−0.0069 (8)	−0.0005 (8)
N1	0.0189 (10)	0.0212 (10)	0.0183 (10)	−0.0016 (8)	0.0001 (7)	0.0018 (8)
N2	0.0347 (13)	0.0338 (13)	0.0360 (13)	0.0014 (11)	−0.0033 (10)	0.0151 (10)
N3	0.0515 (15)	0.0219 (12)	0.0366 (13)	0.0032 (11)	−0.0013 (11)	−0.0022 (9)
C1	0.0161 (11)	0.0223 (12)	0.0195 (11)	−0.0022 (9)	0.0010 (9)	−0.0001 (9)
C2	0.0198 (11)	0.0175 (12)	0.0231 (12)	−0.0018 (9)	0.0003 (9)	−0.0004 (9)
C3	0.0155 (11)	0.0227 (12)	0.0208 (11)	−0.0013 (9)	−0.0003 (9)	0.0024 (9)
C4	0.0187 (11)	0.0230 (12)	0.0179 (11)	−0.0019 (9)	−0.0020 (9)	0.0001 (9)
C5	0.0178 (11)	0.0194 (12)	0.0211 (11)	−0.0033 (9)	0.0003 (9)	0.0017 (9)
C6	0.0202 (12)	0.0213 (12)	0.0217 (12)	0.0020 (10)	−0.0021 (9)	0.0004 (10)
C7	0.0187 (11)	0.0215 (12)	0.0183 (11)	0.0040 (9)	−0.0014 (9)	−0.0001 (9)
C8	0.0196 (11)	0.0247 (13)	0.0217 (11)	0.0013 (9)	0.0007 (9)	−0.0017 (10)
C9	0.0253 (12)	0.0242 (13)	0.0294 (13)	−0.0001 (10)	0.0057 (11)	0.0035 (10)
C10	0.0345 (14)	0.0326 (14)	0.0217 (12)	0.0038 (12)	0.0047 (11)	0.0075 (11)
C11	0.0375 (15)	0.0333 (14)	0.0175 (12)	0.0053 (12)	−0.0012 (10)	−0.0018 (11)
C12	0.0262 (12)	0.0211 (12)	0.0218 (12)	0.0030 (10)	−0.0012 (10)	−0.0008 (10)
C13	0.0183 (11)	0.0207 (11)	0.0232 (11)	−0.0019 (9)	−0.0035 (9)	0.0032 (10)
C14	0.0312 (13)	0.0259 (13)	0.0272 (13)	0.0026 (11)	−0.0017 (11)	0.0020 (10)
C15	0.0371 (15)	0.0257 (14)	0.0423 (16)	0.0063 (12)	−0.0035 (13)	0.0064 (12)
C16	0.0299 (14)	0.0412 (16)	0.0235 (13)	−0.0002 (12)	−0.0019 (11)	0.0080 (12)
C17	0.0243 (13)	0.0267 (14)	0.0233 (12)	0.0018 (10)	−0.0031 (10)	0.0010 (10)
C18	0.0195 (12)	0.0209 (12)	0.0209 (11)	−0.0032 (10)	−0.0040 (9)	−0.0004 (9)
C19	0.0304 (13)	0.0226 (12)	0.0226 (12)	−0.0020 (10)	−0.0026 (10)	0.0011 (10)
C20	0.0436 (15)	0.0279 (14)	0.0283 (13)	0.0019 (12)	0.0018 (12)	−0.0040 (11)
C21	0.0444 (17)	0.0220 (13)	0.0299 (13)	−0.0020 (12)	−0.0046 (12)	0.0047 (11)
C22	0.0315 (13)	0.0227 (13)	0.0208 (12)	−0.0013 (10)	−0.0006 (10)	0.0011 (9)

Geometric parameters (Å, º) top

O1—C6	1.237 (3)	C9—C10	1.396 (3)
O2—C12	1.351 (3)	C9—H9	0.9500
O2—H2'	0.87 (3)	C10—C11	1.372 (4)
N1—C1	1.342 (3)	C10—H10	0.9500
N1—C5	1.351 (3)	C11—C12	1.388 (3)
N2—C16	1.334 (3)	C11—H11	0.9500
N2—C15	1.338 (3)	C13—C14	1.389 (3)
N3—C20	1.338 (3)	C13—C17	1.392 (3)
N3—C21	1.343 (3)	C14—C15	1.388 (3)
C1—C2	1.386 (3)	C14—H14	0.9500
C1—C6	1.509 (3)	C15—H15	0.9500
C2—C3	1.392 (3)	C16—C17	1.381 (3)
C2—H2	0.9500	C16—H16	0.9500
C3—C4	1.395 (3)	C17—H17	0.9500
C3—C13	1.487 (3)	C18—C19	1.390 (3)
C4—C5	1.395 (3)	C18—C22	1.391 (3)
C4—H4	0.9500	C19—C20	1.380 (3)
C5—C18	1.484 (3)	C19—H19	0.9500
C6—C7	1.467 (3)	C20—H20	0.9500
C7—C8	1.404 (3)	C21—C22	1.381 (4)
C7—C12	1.419 (3)	C21—H21	0.9500
C8—C9	1.379 (3)	C22—H22	0.9500
C8—H8	0.9500

C12—O2—H2'	105 (2)	C10—C11—H11	119.9
C1—N1—C5	116.96 (19)	C12—C11—H11	119.9
C16—N2—C15	115.9 (2)	O2—C12—C11	117.7 (2)
C20—N3—C21	115.7 (2)	O2—C12—C7	122.0 (2)
N1—C1—C2	124.1 (2)	C11—C12—C7	120.3 (2)
N1—C1—C6	117.72 (19)	C14—C13—C17	117.1 (2)
C2—C1—C6	118.1 (2)	C14—C13—C3	122.4 (2)
C1—C2—C3	119.3 (2)	C17—C13—C3	120.6 (2)
C1—C2—H2	120.4	C15—C14—C13	119.2 (2)
C3—C2—H2	120.4	C15—C14—H14	120.4
C2—C3—C4	117.1 (2)	C13—C14—H14	120.4
C2—C3—C13	121.9 (2)	N2—C15—C14	124.1 (2)
C4—C3—C13	120.9 (2)	N2—C15—H15	117.9
C3—C4—C5	120.2 (2)	C14—C15—H15	117.9
C3—C4—H4	119.9	N2—C16—C17	124.4 (2)
C5—C4—H4	119.9	N2—C16—H16	117.8
N1—C5—C4	122.3 (2)	C17—C16—H16	117.8
N1—C5—C18	115.6 (2)	C16—C17—C13	119.3 (2)
C4—C5—C18	122.1 (2)	C16—C17—H17	120.3
O1—C6—C7	121.0 (2)	C13—C17—H17	120.3
O1—C6—C1	115.9 (2)	C19—C18—C22	116.9 (2)
C7—C6—C1	123.0 (2)	C19—C18—C5	122.1 (2)
C8—C7—C12	117.8 (2)	C22—C18—C5	120.9 (2)
C8—C7—C6	123.5 (2)	C20—C19—C18	119.4 (2)
C12—C7—C6	118.7 (2)	C20—C19—H19	120.3
C9—C8—C7	121.4 (2)	C18—C19—H19	120.3
C9—C8—H8	119.3	N3—C20—C19	124.4 (2)
C7—C8—H8	119.3	N3—C20—H20	117.8
C8—C9—C10	119.4 (2)	C19—C20—H20	117.8
C8—C9—H9	120.3	N3—C21—C22	124.2 (2)
C10—C9—H9	120.3	N3—C21—H21	117.9
C11—C10—C9	120.8 (2)	C22—C21—H21	117.9
C11—C10—H10	119.6	C21—C22—C18	119.5 (2)
C9—C10—H10	119.6	C21—C22—H22	120.3
C10—C11—C12	120.2 (2)	C18—C22—H22	120.3

C5—N1—C1—C2	0.2 (3)	C6—C7—C12—O2	0.1 (3)
C5—N1—C1—C6	−175.1 (2)	C8—C7—C12—C11	1.9 (3)
N1—C1—C2—C3	2.1 (3)	C6—C7—C12—C11	179.6 (2)
C6—C1—C2—C3	177.4 (2)	C2—C3—C13—C14	−24.2 (3)
C1—C2—C3—C4	−2.1 (3)	C4—C3—C13—C14	158.0 (2)
C1—C2—C3—C13	180.0 (2)	C2—C3—C13—C17	155.4 (2)
C2—C3—C4—C5	0.1 (3)	C4—C3—C13—C17	−22.4 (3)
C13—C3—C4—C5	178.0 (2)	C17—C13—C14—C15	0.8 (4)
C1—N1—C5—C4	−2.3 (3)	C3—C13—C14—C15	−179.6 (2)
C1—N1—C5—C18	175.8 (2)	C16—N2—C15—C14	−0.8 (4)
C3—C4—C5—N1	2.2 (3)	C13—C14—C15—N2	−0.1 (4)
C3—C4—C5—C18	−175.8 (2)	C15—N2—C16—C17	1.0 (4)
N1—C1—C6—O1	143.3 (2)	N2—C16—C17—C13	−0.3 (4)
C2—C1—C6—O1	−32.3 (3)	C14—C13—C17—C16	−0.7 (3)
N1—C1—C6—C7	−37.6 (3)	C3—C13—C17—C16	179.7 (2)
C2—C1—C6—C7	146.9 (2)	N1—C5—C18—C19	−151.7 (2)
O1—C6—C7—C8	173.4 (2)	C4—C5—C18—C19	26.4 (3)
C1—C6—C7—C8	−5.7 (3)	N1—C5—C18—C22	24.9 (3)
O1—C6—C7—C12	−4.2 (3)	C4—C5—C18—C22	−157.0 (2)
C1—C6—C7—C12	176.7 (2)	C22—C18—C19—C20	−0.7 (4)
C12—C7—C8—C9	−1.3 (3)	C5—C18—C19—C20	176.0 (2)
C6—C7—C8—C9	−178.9 (2)	C21—N3—C20—C19	0.9 (4)
C7—C8—C9—C10	0.1 (3)	C18—C19—C20—N3	−0.3 (4)
C8—C9—C10—C11	0.5 (4)	C20—N3—C21—C22	−0.5 (4)
C9—C10—C11—C12	0.1 (4)	N3—C21—C22—C18	−0.4 (4)
C10—C11—C12—O2	178.2 (2)	C19—C18—C22—C21	1.1 (4)
C10—C11—C12—C7	−1.3 (4)	C5—C18—C22—C21	−175.7 (2)
C8—C7—C12—O2	−177.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2′···O1	0.87 (4)	1.73 (4)	2.527 (3)	152 (3)
C16—H16···O2ⁱ	0.95	2.59	3.309 (3)	132
C17—H17···N2ⁱⁱ	0.95	2.49	3.344 (3)	150
C21—H21···O1ⁱⁱⁱ	0.95	2.45	3.380 (3)	165

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

References

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