Structures and photophysical properties of two luminescent bi­pyridine com­pounds: 2′,6′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine and 2′,6′-dimeth­oxy-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine

The title com­pounds, C₂₁H₁₃F₂N₃O (1) and C₂₃H₁₉N₃O₃ (2), have been synthesized by typical cross-coupling reactions. Both com­pounds have been characterized by single-crystal X-ray diffraction. Bi­pyridine 1 exhibits a fully extended structure in which the terminal pyridine rings are oriented away from each other, while bi­pyridine 2 displays a bent structure in which terminal pyridine rings are oriented in the same direction. Several inter­molecular inter­actions lead to the formation of two- and three-dimensional supra­molecular networks in the crystal structures of 1 and 2, respectively. Com­pound 1 bears fluorine substituents and emits a strong fluorescence with λ_max = 325 nm, while meth­oxy-substituted com­pound 2 displays red-shifted emissions with λ_max = 366 nm. The emissions observed in both com­pounds originate from phenyl- and 2,3′-bi­pyridine-based π–π* transitions, according to theoretical calculations. Both com­pounds have high triplet energies (T₁) ranging from 2.64 to 2.65 eV, which makes them potential host materials in organic light-emitting diodes (OLEDs).

Computing details

For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

2',6'-Difluoro-6-[3-(pyridin-2-yloxy)phenyl]-2,3'-bipyridine (1)

Crystal data

C21H13F2N3O	F(000) = 744
Mr = 361.34	Dx = 1.464 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8772 (3) Å	Cell parameters from 5436 reflections
b = 17.2089 (4) Å	θ = 2.4–28.3°
c = 8.4838 (2) Å	µ = 0.11 mm^−1
β = 109.0219 (6)°	T = 173 K
V = 1639.34 (7) Å^3	Block, colourless
Z = 4	0.54 × 0.33 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer	3356 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 28.3°, θmin = 1.8°
Tmin = 0.708, Tmax = 0.746	h = −15→15
16583 measured reflections	k = −22→20
4072 independent reflections	l = −11→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0545P)^2 + 0.4711P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4072 reflections	Δρmax = 0.27 e Å^−3
244 parameters	Δρmin = −0.28 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
F1	0.00226 (8)	0.04336 (5)	0.25742 (11)	0.0482 (2)
F2	0.25997 (10)	−0.11345 (5)	0.61756 (13)	0.0566 (3)
O1	0.26047 (8)	0.58488 (5)	0.63287 (13)	0.0374 (2)
N1	0.42580 (10)	0.58422 (6)	0.54525 (14)	0.0334 (2)
N2	0.16004 (9)	0.24143 (6)	0.53616 (13)	0.0270 (2)
N3	0.13118 (11)	−0.03261 (7)	0.44194 (16)	0.0400 (3)
C1	0.49955 (13)	0.62502 (8)	0.48535 (18)	0.0373 (3)
H1	0.5624	0.5980	0.4627	0.045*
C2	0.48915 (13)	0.70374 (8)	0.45495 (19)	0.0398 (3)
H2	0.5437	0.7305	0.4135	0.048*
C3	0.39665 (13)	0.74282 (8)	0.48667 (19)	0.0401 (3)
H3	0.3864	0.7970	0.4659	0.048*
C4	0.32007 (12)	0.70286 (7)	0.54810 (17)	0.0337 (3)
H4	0.2563	0.7283	0.5716	0.040*
C5	0.33978 (11)	0.62344 (7)	0.57457 (15)	0.0280 (3)
C6	0.27979 (11)	0.50591 (7)	0.67107 (17)	0.0304 (3)
C7	0.20272 (11)	0.45333 (7)	0.56861 (15)	0.0275 (3)
H7	0.1431	0.4705	0.4700	0.033*
C8	0.21257 (10)	0.37420 (7)	0.61041 (15)	0.0250 (2)
C9	0.30060 (11)	0.35069 (7)	0.75536 (15)	0.0292 (3)
H9	0.3084	0.2973	0.7853	0.035*
C10	0.37706 (12)	0.40482 (8)	0.85636 (18)	0.0376 (3)
H10	0.4368	0.3882	0.9554	0.045*
C11	0.36737 (12)	0.48301 (8)	0.81459 (18)	0.0375 (3)
H11	0.4201	0.5200	0.8837	0.045*
C12	0.12875 (10)	0.31611 (7)	0.50455 (14)	0.0266 (2)
C13	0.02336 (12)	0.33781 (8)	0.38157 (17)	0.0355 (3)
H13	0.0026	0.3910	0.3611	0.043*
C14	−0.04995 (12)	0.28023 (9)	0.29045 (19)	0.0415 (3)
H14	−0.1218	0.2936	0.2051	0.050*
C15	−0.01913 (12)	0.20325 (8)	0.32308 (18)	0.0384 (3)
H15	−0.0694	0.1631	0.2618	0.046*
C16	0.08755 (11)	0.18564 (7)	0.44801 (15)	0.0294 (3)
C17	0.13192 (12)	0.10536 (7)	0.49736 (16)	0.0307 (3)
C18	0.09119 (12)	0.03863 (8)	0.40363 (17)	0.0347 (3)
C19	0.21866 (14)	−0.04036 (7)	0.58170 (19)	0.0397 (3)
C20	0.27069 (15)	0.01846 (8)	0.69145 (18)	0.0414 (3)
H20	0.3342	0.0091	0.7919	0.050*
C21	0.22451 (13)	0.09189 (7)	0.64592 (16)	0.0362 (3)
H21	0.2567	0.1344	0.7178	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0400 (5)	0.0486 (5)	0.0477 (5)	−0.0094 (4)	0.0026 (4)	−0.0194 (4)
F2	0.0801 (7)	0.0235 (4)	0.0678 (6)	0.0032 (4)	0.0265 (5)	−0.0015 (4)
O1	0.0343 (5)	0.0218 (4)	0.0600 (6)	0.0043 (3)	0.0210 (5)	0.0041 (4)
N1	0.0330 (6)	0.0261 (5)	0.0412 (6)	0.0039 (4)	0.0123 (5)	0.0008 (4)
N2	0.0281 (5)	0.0263 (5)	0.0258 (5)	−0.0019 (4)	0.0077 (4)	−0.0004 (4)
N3	0.0473 (7)	0.0298 (6)	0.0486 (7)	−0.0104 (5)	0.0237 (6)	−0.0113 (5)
C1	0.0339 (7)	0.0362 (7)	0.0438 (8)	0.0035 (5)	0.0153 (6)	0.0014 (6)
C2	0.0410 (7)	0.0360 (7)	0.0440 (8)	−0.0050 (6)	0.0161 (6)	0.0017 (6)
C3	0.0482 (8)	0.0239 (6)	0.0478 (8)	−0.0016 (5)	0.0151 (7)	0.0002 (5)
C4	0.0357 (7)	0.0232 (6)	0.0415 (7)	0.0032 (5)	0.0117 (6)	−0.0025 (5)
C5	0.0271 (6)	0.0235 (5)	0.0302 (6)	−0.0002 (4)	0.0052 (5)	−0.0024 (4)
C6	0.0301 (6)	0.0224 (6)	0.0416 (7)	0.0027 (4)	0.0157 (5)	0.0020 (5)
C7	0.0258 (6)	0.0271 (6)	0.0301 (6)	0.0038 (4)	0.0097 (5)	0.0031 (4)
C8	0.0246 (5)	0.0247 (5)	0.0268 (6)	0.0013 (4)	0.0098 (5)	0.0006 (4)
C9	0.0295 (6)	0.0243 (5)	0.0311 (6)	0.0009 (5)	0.0062 (5)	0.0024 (5)
C10	0.0348 (7)	0.0312 (6)	0.0370 (7)	−0.0002 (5)	−0.0017 (6)	0.0005 (5)
C11	0.0338 (7)	0.0277 (6)	0.0445 (8)	−0.0033 (5)	0.0039 (6)	−0.0050 (5)
C12	0.0258 (6)	0.0283 (6)	0.0257 (6)	0.0002 (4)	0.0086 (5)	0.0013 (4)
C13	0.0302 (6)	0.0327 (6)	0.0380 (7)	0.0020 (5)	0.0035 (5)	0.0032 (5)
C14	0.0290 (7)	0.0449 (8)	0.0407 (8)	−0.0004 (6)	−0.0021 (6)	0.0020 (6)
C15	0.0314 (7)	0.0398 (7)	0.0378 (7)	−0.0086 (5)	0.0026 (6)	−0.0045 (6)
C16	0.0304 (6)	0.0304 (6)	0.0275 (6)	−0.0047 (5)	0.0098 (5)	−0.0015 (5)
C17	0.0358 (6)	0.0276 (6)	0.0301 (6)	−0.0062 (5)	0.0129 (5)	−0.0033 (5)
C18	0.0347 (7)	0.0357 (7)	0.0357 (7)	−0.0105 (5)	0.0143 (6)	−0.0086 (5)
C19	0.0561 (9)	0.0238 (6)	0.0456 (8)	−0.0034 (6)	0.0255 (7)	−0.0018 (5)
C20	0.0600 (9)	0.0286 (6)	0.0338 (7)	0.0000 (6)	0.0128 (7)	0.0018 (5)
C21	0.0523 (8)	0.0251 (6)	0.0289 (6)	−0.0035 (5)	0.0100 (6)	−0.0023 (5)

Geometric parameters (Å, º)

F1—C18	1.3442 (16)	C8—C9	1.3895 (16)
F2—C19	1.3484 (16)	C8—C12	1.4880 (16)
O1—C5	1.3697 (15)	C9—C10	1.3854 (18)
O1—C6	1.3985 (14)	C9—H9	0.9500
N1—C5	1.3140 (16)	C10—C11	1.3867 (18)
N1—C1	1.3449 (18)	C10—H10	0.9500
N2—C12	1.3405 (15)	C11—H11	0.9500
N2—C16	1.3425 (15)	C12—C13	1.3941 (17)
N3—C19	1.304 (2)	C13—C14	1.3779 (19)
N3—C18	1.3166 (19)	C13—H13	0.9500
C1—C2	1.3770 (19)	C14—C15	1.378 (2)
C1—H1	0.9500	C14—H14	0.9500
C2—C3	1.387 (2)	C15—C16	1.3947 (18)
C2—H2	0.9500	C15—H15	0.9500
C3—C4	1.371 (2)	C16—C17	1.4893 (18)
C3—H3	0.9500	C17—C18	1.3908 (17)
C4—C5	1.3925 (17)	C17—C21	1.3957 (19)
C4—H4	0.9500	C19—C20	1.378 (2)
C6—C7	1.3762 (17)	C20—C21	1.3816 (19)
C6—C11	1.3763 (19)	C20—H20	0.9500
C7—C8	1.4024 (16)	C21—H21	0.9500
C7—H7	0.9500
C5—O1—C6	118.31 (9)	C6—C11—C10	118.67 (12)
C5—N1—C1	116.47 (11)	C6—C11—H11	120.7
C12—N2—C16	119.24 (11)	C10—C11—H11	120.7
C19—N3—C18	115.85 (12)	N2—C12—C13	121.96 (11)
N1—C1—C2	123.68 (13)	N2—C12—C8	115.85 (10)
N1—C1—H1	118.2	C13—C12—C8	122.19 (11)
C2—C1—H1	118.2	C14—C13—C12	118.45 (12)
C1—C2—C3	117.97 (13)	C14—C13—H13	120.8
C1—C2—H2	121.0	C12—C13—H13	120.8
C3—C2—H2	121.0	C13—C14—C15	120.04 (12)
C4—C3—C2	119.72 (12)	C13—C14—H14	120.0
C4—C3—H3	120.1	C15—C14—H14	120.0
C2—C3—H3	120.1	C14—C15—C16	118.52 (12)
C3—C4—C5	117.13 (12)	C14—C15—H15	120.7
C3—C4—H4	121.4	C16—C15—H15	120.7
C5—C4—H4	121.4	N2—C16—C15	121.79 (12)
N1—C5—O1	119.22 (11)	N2—C16—C17	113.75 (11)
N1—C5—C4	125.02 (12)	C15—C16—C17	124.46 (11)
O1—C5—C4	115.75 (11)	C18—C17—C21	113.83 (12)
C7—C6—C11	121.72 (11)	C18—C17—C16	125.45 (12)
C7—C6—O1	117.87 (11)	C21—C17—C16	120.69 (11)
C11—C6—O1	120.19 (12)	N3—C18—F1	113.33 (11)
C6—C7—C8	119.69 (11)	N3—C18—C17	126.68 (13)
C6—C7—H7	120.2	F1—C18—C17	119.99 (13)
C8—C7—H7	120.2	N3—C19—F2	115.09 (12)
C9—C8—C7	118.89 (11)	N3—C19—C20	126.04 (13)
C9—C8—C12	120.07 (10)	F2—C19—C20	118.86 (14)
C7—C8—C12	121.02 (11)	C19—C20—C21	115.67 (14)
C10—C9—C8	120.27 (11)	C19—C20—H20	122.2
C10—C9—H9	119.9	C21—C20—H20	122.2
C8—C9—H9	119.9	C20—C21—C17	121.90 (12)
C9—C10—C11	120.75 (12)	C20—C21—H21	119.0
C9—C10—H10	119.6	C17—C21—H21	119.0
C11—C10—H10	119.6
C5—N1—C1—C2	0.2 (2)	C7—C8—C12—C13	−13.76 (18)
N1—C1—C2—C3	−0.6 (2)	N2—C12—C13—C14	−0.1 (2)
C1—C2—C3—C4	0.7 (2)	C8—C12—C13—C14	−179.23 (13)
C2—C3—C4—C5	−0.4 (2)	C12—C13—C14—C15	0.7 (2)
C1—N1—C5—O1	178.84 (12)	C13—C14—C15—C16	−0.7 (2)
C1—N1—C5—C4	0.1 (2)	C12—N2—C16—C15	0.62 (18)
C6—O1—C5—N1	4.82 (17)	C12—N2—C16—C17	−179.11 (10)
C6—O1—C5—C4	−176.32 (12)	C14—C15—C16—N2	0.0 (2)
C3—C4—C5—N1	0.0 (2)	C14—C15—C16—C17	179.69 (13)
C3—C4—C5—O1	−178.77 (12)	N2—C16—C17—C18	−163.70 (12)
C5—O1—C6—C7	−109.75 (13)	C15—C16—C17—C18	16.6 (2)
C5—O1—C6—C11	75.49 (16)	N2—C16—C17—C21	14.11 (17)
C11—C6—C7—C8	0.18 (19)	C15—C16—C17—C21	−165.60 (13)
O1—C6—C7—C8	−174.50 (11)	C19—N3—C18—F1	179.14 (12)
C6—C7—C8—C9	−0.01 (18)	C19—N3—C18—C17	−0.7 (2)
C6—C7—C8—C12	178.47 (11)	C21—C17—C18—N3	−0.1 (2)
C7—C8—C9—C10	0.01 (18)	C16—C17—C18—N3	177.85 (13)
C12—C8—C9—C10	−178.49 (12)	C21—C17—C18—F1	−179.90 (12)
C8—C9—C10—C11	−0.2 (2)	C16—C17—C18—F1	−2.0 (2)
C7—C6—C11—C10	−0.3 (2)	C18—N3—C19—F2	−178.85 (12)
O1—C6—C11—C10	174.22 (13)	C18—N3—C19—C20	0.9 (2)
C9—C10—C11—C6	0.3 (2)	N3—C19—C20—C21	−0.2 (2)
C16—N2—C12—C13	−0.55 (18)	F2—C19—C20—C21	179.45 (13)
C16—N2—C12—C8	178.61 (10)	C19—C20—C21—C17	−0.6 (2)
C9—C8—C12—N2	−14.46 (16)	C18—C17—C21—C20	0.8 (2)
C7—C8—C12—N2	167.08 (11)	C16—C17—C21—C20	−177.29 (13)
C9—C8—C12—C13	164.70 (12)

Hydrogen-bond geometry (Å, º)

Cg4 is the centroid of the C6–C11 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F1^i	0.95	2.47	3.4043 (14)	168
C15—H15···F1	0.95	2.23	2.8351 (17)	120
C20—H20···N1^ii	0.95	2.62	3.4527 (18)	147
C1—H1···Cg4^iii	0.95	2.68	3.5583 (17)	153

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

2',6'-Dimethoxy-6-[3-(pyridin-2-yloxy)phenyl]-2,3'-bipyridine (2)

Crystal data

C23H19N3O3	F(000) = 1616
Mr = 385.41	Dx = 1.386 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.0396 (3) Å	Cell parameters from 5646 reflections
b = 7.9410 (1) Å	θ = 2.8–28.0°
c = 22.5109 (3) Å	µ = 0.09 mm^−1
β = 100.8986 (7)°	T = 173 K
V = 3693.18 (9) Å^3	Plate, colourless
Z = 8	0.34 × 0.25 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer	3745 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.027
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 28.3°, θmin = 1.8°
Tmin = 0.695, Tmax = 0.746	h = −28→27
18253 measured reflections	k = −8→10
4570 independent reflections	l = −26→29

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 2.1417P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4570 reflections	Δρmax = 0.24 e Å^−3
264 parameters	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.07875 (4)	−0.11852 (11)	0.29652 (4)	0.0307 (2)
O2	0.89080 (5)	0.27576 (12)	−0.07287 (4)	0.0348 (2)
O3	0.72822 (5)	−0.03111 (14)	−0.01649 (4)	0.0415 (3)
N1	1.11367 (5)	−0.38709 (14)	0.27693 (5)	0.0314 (2)
N2	1.02027 (5)	0.12262 (12)	0.08854 (4)	0.0236 (2)
N3	0.81073 (5)	0.12442 (13)	−0.04251 (5)	0.0286 (2)
C1	1.10697 (8)	−0.55456 (18)	0.28401 (6)	0.0389 (3)
H1	1.1336	−0.6279	0.2660	0.047*
C2	1.06409 (8)	−0.62517 (19)	0.31568 (7)	0.0411 (3)
H2	1.0611	−0.7439	0.3194	0.049*
C3	1.02519 (7)	−0.51843 (19)	0.34210 (6)	0.0384 (3)
H3	0.9949	−0.5633	0.3643	0.046*
C4	1.03082 (6)	−0.34744 (18)	0.33580 (6)	0.0317 (3)
H4	1.0051	−0.2712	0.3536	0.038*
C5	1.07566 (6)	−0.29023 (15)	0.30236 (5)	0.0256 (3)
C6	1.11613 (6)	−0.04857 (15)	0.25739 (5)	0.0266 (3)
C7	1.08353 (6)	0.01403 (14)	0.20277 (5)	0.0239 (2)
H7	1.0380	0.0005	0.1915	0.029*
C8	1.11790 (6)	0.09729 (15)	0.16414 (5)	0.0241 (2)
C9	1.18479 (6)	0.11608 (17)	0.18279 (6)	0.0303 (3)
H9	1.2090	0.1723	0.1571	0.036*
C10	1.21640 (6)	0.05407 (19)	0.23805 (6)	0.0359 (3)
H10	1.2618	0.0688	0.2500	0.043*
C11	1.18208 (7)	−0.02940 (18)	0.27592 (6)	0.0338 (3)
H11	1.2035	−0.0725	0.3138	0.041*
C12	1.08304 (6)	0.16460 (14)	0.10513 (5)	0.0237 (2)
C13	1.11393 (6)	0.26932 (16)	0.06985 (6)	0.0309 (3)
H13	1.1585	0.2964	0.0820	0.037*
C14	1.07846 (7)	0.33250 (18)	0.01702 (6)	0.0373 (3)
H14	1.0982	0.4061	−0.0074	0.045*
C15	1.01436 (7)	0.28939 (17)	−0.00067 (6)	0.0322 (3)
H15	0.9898	0.3315	−0.0374	0.039*
C16	0.98589 (6)	0.18298 (14)	0.03613 (5)	0.0236 (2)
C17	0.91694 (6)	0.13012 (15)	0.02152 (5)	0.0243 (2)
C18	0.87195 (6)	0.17508 (15)	−0.03084 (5)	0.0260 (3)
C19	0.79006 (6)	0.02415 (17)	−0.00335 (6)	0.0308 (3)
C20	0.82882 (6)	−0.02888 (18)	0.05031 (6)	0.0331 (3)
H20	0.8125	−0.0999	0.0779	0.040*
C21	0.89199 (6)	0.02606 (16)	0.06171 (6)	0.0289 (3)
H21	0.9196	−0.0079	0.0981	0.035*
C22	0.84200 (7)	0.32444 (18)	−0.12389 (6)	0.0380 (3)
H22A	0.8611	0.4003	−0.1501	0.057*
H22B	0.8066	0.3823	−0.1095	0.057*
H22C	0.8251	0.2239	−0.1468	0.057*
C23	0.69086 (7)	0.0250 (2)	−0.07340 (6)	0.0427 (4)
H23A	0.6496	−0.0357	−0.0818	0.064*
H23B	0.7150	0.0027	−0.1058	0.064*
H23C	0.6826	0.1461	−0.0714	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0348 (5)	0.0297 (5)	0.0299 (5)	0.0042 (4)	0.0119 (4)	0.0033 (3)
O2	0.0369 (5)	0.0394 (5)	0.0253 (4)	−0.0058 (4)	−0.0012 (4)	0.0098 (4)
O3	0.0258 (5)	0.0606 (7)	0.0361 (5)	−0.0074 (4)	0.0009 (4)	0.0069 (5)
N1	0.0322 (6)	0.0334 (6)	0.0278 (5)	0.0024 (4)	0.0037 (4)	−0.0019 (4)
N2	0.0237 (5)	0.0246 (5)	0.0227 (5)	−0.0007 (4)	0.0047 (4)	−0.0018 (4)
N3	0.0273 (6)	0.0321 (6)	0.0253 (5)	0.0011 (4)	0.0025 (4)	−0.0014 (4)
C1	0.0437 (8)	0.0338 (7)	0.0383 (7)	0.0041 (6)	0.0051 (6)	−0.0056 (6)
C2	0.0457 (9)	0.0309 (7)	0.0432 (8)	−0.0037 (6)	0.0000 (6)	0.0018 (6)
C3	0.0331 (7)	0.0421 (8)	0.0384 (7)	−0.0049 (6)	0.0023 (6)	0.0098 (6)
C4	0.0263 (6)	0.0388 (7)	0.0290 (6)	0.0040 (5)	0.0031 (5)	0.0061 (5)
C5	0.0241 (6)	0.0302 (6)	0.0203 (5)	0.0016 (5)	−0.0017 (4)	0.0020 (4)
C6	0.0278 (6)	0.0266 (6)	0.0265 (6)	0.0007 (5)	0.0081 (5)	−0.0015 (5)
C7	0.0217 (6)	0.0237 (6)	0.0261 (6)	−0.0012 (4)	0.0039 (4)	−0.0040 (4)
C8	0.0235 (6)	0.0233 (6)	0.0258 (6)	−0.0016 (4)	0.0051 (4)	−0.0049 (4)
C9	0.0241 (6)	0.0343 (7)	0.0331 (6)	−0.0041 (5)	0.0065 (5)	−0.0015 (5)
C10	0.0213 (6)	0.0465 (8)	0.0378 (7)	−0.0016 (5)	−0.0001 (5)	−0.0022 (6)
C11	0.0288 (7)	0.0422 (8)	0.0282 (6)	0.0025 (5)	0.0000 (5)	0.0018 (5)
C12	0.0241 (6)	0.0220 (5)	0.0256 (6)	−0.0011 (4)	0.0066 (4)	−0.0047 (4)
C13	0.0260 (6)	0.0312 (7)	0.0361 (7)	−0.0060 (5)	0.0070 (5)	0.0001 (5)
C14	0.0368 (8)	0.0389 (8)	0.0381 (7)	−0.0065 (6)	0.0117 (6)	0.0097 (6)
C15	0.0337 (7)	0.0343 (7)	0.0287 (6)	−0.0012 (5)	0.0063 (5)	0.0062 (5)
C16	0.0269 (6)	0.0217 (5)	0.0225 (5)	0.0010 (4)	0.0056 (4)	−0.0023 (4)
C17	0.0248 (6)	0.0254 (6)	0.0225 (5)	0.0013 (4)	0.0038 (4)	−0.0015 (4)
C18	0.0305 (6)	0.0249 (6)	0.0225 (5)	0.0005 (5)	0.0045 (5)	−0.0015 (4)
C19	0.0253 (6)	0.0373 (7)	0.0295 (6)	−0.0003 (5)	0.0044 (5)	−0.0025 (5)
C20	0.0287 (7)	0.0419 (8)	0.0295 (6)	−0.0032 (5)	0.0071 (5)	0.0066 (5)
C21	0.0274 (6)	0.0344 (7)	0.0243 (6)	0.0008 (5)	0.0035 (5)	0.0032 (5)
C22	0.0451 (8)	0.0373 (7)	0.0274 (6)	−0.0024 (6)	−0.0041 (6)	0.0070 (5)
C23	0.0262 (7)	0.0662 (10)	0.0329 (7)	−0.0044 (7)	−0.0014 (6)	0.0013 (7)

Geometric parameters (Å, º)

O1—C5	1.3726 (15)	C9—C10	1.3853 (19)
O1—C6	1.4018 (15)	C9—H9	0.9500
O2—C18	1.3540 (15)	C10—C11	1.386 (2)
O2—C22	1.4411 (15)	C10—H10	0.9500
O3—C19	1.3518 (16)	C11—H11	0.9500
O3—C23	1.4412 (17)	C12—C13	1.3928 (17)
N1—C5	1.3159 (16)	C13—C14	1.3738 (19)
N1—C1	1.3499 (18)	C13—H13	0.9500
N2—C12	1.3446 (15)	C14—C15	1.3752 (19)
N2—C16	1.3498 (15)	C14—H14	0.9500
N3—C19	1.3210 (17)	C15—C16	1.3952 (17)
N3—C18	1.3274 (16)	C15—H15	0.9500
C1—C2	1.371 (2)	C16—C17	1.4861 (16)
C1—H1	0.9500	C17—C21	1.3988 (17)
C2—C3	1.388 (2)	C17—C18	1.4109 (16)
C2—H2	0.9500	C19—C20	1.3887 (18)
C3—C4	1.373 (2)	C20—C21	1.3762 (18)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.3900 (18)	C21—H21	0.9500
C4—H4	0.9500	C22—H22A	0.9800
C6—C11	1.3797 (18)	C22—H22B	0.9800
C6—C7	1.3821 (17)	C22—H22C	0.9800
C7—C8	1.3979 (16)	C23—H23A	0.9800
C7—H7	0.9500	C23—H23B	0.9800
C8—C9	1.3985 (17)	C23—H23C	0.9800
C8—C12	1.4900 (16)
C5—O1—C6	119.74 (10)	C13—C12—C8	121.23 (11)
C18—O2—C22	117.17 (10)	C14—C13—C12	118.42 (12)
C19—O3—C23	115.77 (11)	C14—C13—H13	120.8
C5—N1—C1	116.03 (12)	C12—C13—H13	120.8
C12—N2—C16	119.38 (10)	C13—C14—C15	120.14 (12)
C19—N3—C18	118.69 (11)	C13—C14—H14	119.9
N1—C1—C2	123.91 (14)	C15—C14—H14	119.9
N1—C1—H1	118.0	C14—C15—C16	119.11 (12)
C2—C1—H1	118.0	C14—C15—H15	120.4
C1—C2—C3	118.19 (14)	C16—C15—H15	120.4
C1—C2—H2	120.9	N2—C16—C15	120.97 (11)
C3—C2—H2	120.9	N2—C16—C17	115.63 (10)
C4—C3—C2	119.37 (14)	C15—C16—C17	123.39 (11)
C4—C3—H3	120.3	C21—C17—C18	114.54 (11)
C2—C3—H3	120.3	C21—C17—C16	119.58 (10)
C3—C4—C5	117.38 (13)	C18—C17—C16	125.88 (11)
C3—C4—H4	121.3	N3—C18—O2	116.23 (10)
C5—C4—H4	121.3	N3—C18—C17	124.14 (11)
N1—C5—O1	119.69 (11)	O2—C18—C17	119.62 (11)
N1—C5—C4	125.11 (12)	N3—C19—O3	118.31 (11)
O1—C5—C4	115.20 (11)	N3—C19—C20	123.36 (12)
C11—C6—C7	122.07 (12)	O3—C19—C20	118.32 (12)
C11—C6—O1	120.36 (11)	C21—C20—C19	116.98 (12)
C7—C6—O1	117.28 (11)	C21—C20—H20	121.5
C6—C7—C8	119.69 (11)	C19—C20—H20	121.5
C6—C7—H7	120.2	C20—C21—C17	122.27 (11)
C8—C7—H7	120.2	C20—C21—H21	118.9
C7—C8—C9	118.25 (11)	C17—C21—H21	118.9
C7—C8—C12	119.93 (10)	O2—C22—H22A	109.5
C9—C8—C12	121.82 (11)	O2—C22—H22B	109.5
C10—C9—C8	121.11 (12)	H22A—C22—H22B	109.5
C10—C9—H9	119.4	O2—C22—H22C	109.5
C8—C9—H9	119.4	H22A—C22—H22C	109.5
C9—C10—C11	120.33 (12)	H22B—C22—H22C	109.5
C9—C10—H10	119.8	O3—C23—H23A	109.5
C11—C10—H10	119.8	O3—C23—H23B	109.5
C6—C11—C10	118.55 (12)	H23A—C23—H23B	109.5
C6—C11—H11	120.7	O3—C23—H23C	109.5
C10—C11—H11	120.7	H23A—C23—H23C	109.5
N2—C12—C13	121.96 (11)	H23B—C23—H23C	109.5
N2—C12—C8	116.79 (10)
C5—N1—C1—C2	−0.4 (2)	C8—C12—C13—C14	−177.52 (12)
N1—C1—C2—C3	0.0 (2)	C12—C13—C14—C15	−1.3 (2)
C1—C2—C3—C4	0.0 (2)	C13—C14—C15—C16	0.9 (2)
C2—C3—C4—C5	0.45 (19)	C12—N2—C16—C15	−0.63 (17)
C1—N1—C5—O1	−179.03 (11)	C12—N2—C16—C17	−179.94 (10)
C1—N1—C5—C4	0.85 (18)	C14—C15—C16—N2	0.13 (19)
C6—O1—C5—N1	8.09 (16)	C14—C15—C16—C17	179.38 (12)
C6—O1—C5—C4	−171.81 (10)	N2—C16—C17—C21	0.74 (16)
C3—C4—C5—N1	−0.91 (18)	C15—C16—C17—C21	−178.55 (12)
C3—C4—C5—O1	178.98 (11)	N2—C16—C17—C18	−179.09 (11)
C5—O1—C6—C11	−81.79 (15)	C15—C16—C17—C18	1.62 (19)
C5—O1—C6—C7	104.29 (13)	C19—N3—C18—O2	179.12 (11)
C11—C6—C7—C8	1.07 (18)	C19—N3—C18—C17	−0.72 (19)
O1—C6—C7—C8	174.87 (10)	C22—O2—C18—N3	3.22 (16)
C6—C7—C8—C9	−0.74 (17)	C22—O2—C18—C17	−176.94 (11)
C6—C7—C8—C12	179.82 (10)	C21—C17—C18—N3	−0.28 (18)
C7—C8—C9—C10	−0.01 (19)	C16—C17—C18—N3	179.56 (11)
C12—C8—C9—C10	179.42 (12)	C21—C17—C18—O2	179.89 (11)
C8—C9—C10—C11	0.5 (2)	C16—C17—C18—O2	−0.27 (19)
C7—C6—C11—C10	−0.6 (2)	C18—N3—C19—O3	−177.96 (11)
O1—C6—C11—C10	−174.22 (12)	C18—N3—C19—C20	1.3 (2)
C9—C10—C11—C6	−0.2 (2)	C23—O3—C19—N3	0.69 (19)
C16—N2—C12—C13	0.14 (17)	C23—O3—C19—C20	−178.62 (12)
C16—N2—C12—C8	178.57 (10)	N3—C19—C20—C21	−0.9 (2)
C7—C8—C12—N2	−8.13 (16)	O3—C19—C20—C21	178.42 (12)
C9—C8—C12—N2	172.45 (11)	C19—C20—C21—C17	−0.2 (2)
C7—C8—C12—C13	170.31 (11)	C18—C17—C21—C20	0.73 (18)
C9—C8—C12—C13	−9.11 (18)	C16—C17—C21—C20	−179.11 (12)
N2—C12—C13—C14	0.85 (19)

Hydrogen-bond geometry (Å, º)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C5, N2/C12–C16, N3/C17–C21 and C6–C11 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O2	0.95	2.13	2.7954 (16)	126
C21—H21···O1^i	0.95	2.52	3.3375 (15)	144
C1—H1···Cg4^ii	0.95	2.92	3.7500 (15)	146
C3—H3···Cg2^iii	0.95	2.79	3.6829 (15)	157
C22—H22C···Cg4^iv	0.98	2.74	3.5999 (15)	147
C23—H23A···Cg1^v	0.98	2.70	3.3546 (15)	125
C23—H23C···Cg3^vi	0.98	2.78	3.6666 (16)	150

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