Redetermined structure of methyl 3-{4,4-di­fluoro-2-[2-(methoxy­car­bon­yl)­ethyl]-1,3,5,7-tetra­methyl-4-bora-3a,4a-di­aza-s-in­da­cen-6-yl}pro­pion­ate

Schollmeyer, D.; Jochen, M.; Detert, H.

doi:10.1107/S2414314624008848

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 9| September 2024| x240884

https://doi.org/10.1107/S2414314624008848

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Redetermined structure of methyl 3-{4,4-difluoro-2-[2-(methoxycarbonyl)ethyl]-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacen-6-yl}propionate

Dieter Schollmeyer,^a Matthias Jochen ^a and Heiner Detert ^a ^*

^aUniversity of Mainz, Department of Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 5 September 2024; accepted 10 September 2024; online 17 September 2024)

In the title compound, C₂₁H₂₇BF₂N₂O₄, a highly fluorescent boron–dipyrromethene dye, the methylpropionate moieties have different conformations. In the crystal, weak C—H⋯F and C—H⋯O interactions link the molecules. Some optical properties are presented.

Keywords: crystal structure; bodipy dye; boron; fluorine,.

CCDC reference: 2263103

Structure description

Fluorescent dyes are of great interest for labeling for analytics in biology and medicine (e.g., Carpenter & Verkman, 2010 ; He et al., 2003 ; Marfin et al., 2017 ; Namkung et al., 2009 ). Boron–dipyrromethene dyes (bodipy) show high quantum yields and excellent photostability and 9-aryl-substituted compounds have been the most investigated. The syntheses of these dyes usually consist of the condensation of pyrroles with aldehydes. To synthesize 9H-bodipy dyes, orthoformates have been used but here, dimethylformamide is the source of the central carbon atom in the title compound, C₂₁H₂₇BF₂N₂O₄ (I) (Fig. 1).

Figure 1
View of compound I. Displacement ellipsoids are drawn at the 50% probability level.

Despite the high formal symmetry of I, the molecule shows no inherent symmetry in its crystalline form. This is due to the methylpropionate moieties: the C17 branch adopts an all-anti conformation lying to one side of the π-system, while the C11 branch has an s–cis conformation on the other side of the π-system. The dihedral angles of these units with respect to the central fused-ring system are 84.3 (2) (C17 branch) and 74.6 (2)° (C11 branch). The 2,3,4-trisubstitution on the pyrrole rings enlarges the bond angles involving the methyl groups [C6—C5—C25 = 127.7 (4); C6—C7—C26 = 128.3 (4); C2—C1—C23 = 127.9 (4); C2—C3—C24 = 127.9 (4)°]. The near identical B4—N3A [1.537 (6) Å] and B4—N4A [1.535 (6) Å] bond lengths indicate the expected delocalization of charge (compare the chemical scheme).

In the extended structure of I, four molecules fill the unit cell, which are arranged in layers lying parallel to the ac-plane and weak C—H⋯ and C—H⋯O interactions link the molecules ((Fig. 2), Table 1). Within the plane a herringbone pattern is formed and a twofold screw axis relates the molecular entities. These crystallographic results confirm recently reported deposited data (Uppal et al., 2020 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯F9ⁱ	0.98	2.37	3.324 (7)	163
C18—H18A⋯O14ⁱⁱ	0.99	2.57	3.268 (6)	128
C23—H23B⋯O20ⁱⁱⁱ	0.98	2.54	3.470 (7)	158
Symmetry codes: (i) ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Partial packing diagram. View along the a axis.

Synthesis and crystallization

The compound was obtained as a side-product in the condensation of the pyrrole with a formylated cryptand (Jochem et al., 2022 ). To the cryptand (97 mg), containing 5% dimethylformamide (4.9 mg, 0.066 mmol) in dry chloroform (10 ml) was added 3,5-dimethyl-4-(methoxycarbonyl)eth-2-ylpyrrole (65.0 mg, 0.359 mmol). Then, 10 µl of trifluoroacetic acid was added and stirred for 26 h. Diiso-propylethylamine (1 ml) was added followed by dichlorodicyanoquinone (54 mg) and stirred for 2 h. Afterwards, BF₃ diethyl ether solution (40%, 1 ml) was added dropwise and stirred. After complete addition, the mixture slowly turned red–violet and started fluorescing after about one h. After 20 h and addition of water (MilliQ, 20 ml), the organic phase was separated, washed with water and dried over Na₂CO₃. Purification via column chromatography (SiO₂/CH₂Cl₂) led to the title compound being eluated first: it crystallized from chloroform/2-propanol as a red solid (12.5 mg) and was recrystallized readily from the mixed solvents of acetonitrile and methanol. HR–ESI–MS: found: 421.2106 [M + H]⁺, calculated 421.2105 for C₂₁H₂₇BF₂N₂O₄⁺; ¹H NMR (400 MHz, CDCl₃) δ = 6.98 (s, 1H), 3.67 (s, 6H), 2.71 (dd, J = 8.6, 6.9 Hz, 4H), 2.50 (s, 6H), 2.44 (dd, J = 8.6, 7.0 Hz, 4H), 2.19 (s, 6H). ¹³C NMR (101 MHz, CDCl₃) δ = 173.25, 155.23, 137.92, 132.64, 128.15, 119.38, 51.86, 34.27, 19.65, 12.80, 9.71. ¹⁹F NMR (282 MHz, CDCl₃) δ = −146.29 (dd, J = 66.4, 33.2 Hz). Optical properties: the title compound has a high of solubility in a broad range of polar solvents but very limited solubility in toluene and alkanes. Bright sunlight led to photochemical decomposition only in very polar media whereas 10⁻⁵ M solutions in less polar solvents remained stable. The absorption spectra in CH₂Cl₂ shows a peak at 527 nm with emission at 536 nm: increasing solvent polarity provokes bathochromic shifts of max. 3 nm.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₂₇BF₂N₂O₄
M_r	420.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	11.9299 (8), 21.6278 (17), 8.2665 (6)
β (°)	108.251 (6)
V (Å³)	2025.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.10 × 0.04

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Integration (X-RED32; Stoe & Cie, 2020 )
T_min, T_max	0.985, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	9943, 4863, 2663
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.090, 0.238, 1.09
No. of reflections	4863
No. of parameters	277
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.48
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2020), SHELXT2014 (Shelxdrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2263103

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314624008848/hb4485sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624008848/hb4485Isup2.hkl

checkCIF report

Computing details top

Methyl 3-{4,4-difluoro-2-[2-(methoxycarbonyl)ethyl]-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacen-6-yl}propionate top

Crystal data top

C₂₁H₂₇BF₂N₂O₄	F(000) = 888
M_r = 420.25	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9299 (8) Å	Cell parameters from 6884 reflections
b = 21.6278 (17) Å	θ = 2.6–28.3°
c = 8.2665 (6) Å	µ = 0.11 mm⁻¹
β = 108.251 (6)°	T = 120 K
V = 2025.6 (3) Å³	Plate, red
Z = 4	0.20 × 0.10 × 0.04 mm

Data collection top

Stoe IPDS 2T diffractometer	4863 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2663 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.052
rotation method, ω scans	θ_max = 28.2°, θ_min = 2.6°
Absorption correction: integration (XRED32; Stoe & Cie, 2020)	h = −15→15
T_min = 0.985, T_max = 0.995	k = −26→28
9943 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.090	H-atom parameters constrained
wR(F²) = 0.238	w = 1/[σ²(F_o²) + (0.0569P)² + 5.4328P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4863 reflections	Δρ_max = 0.50 e Å⁻³
277 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints

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. Hydrogen atoms attached to carbon atoms were placed at calculated positions and were refined in the riding-model approximation with C—H = 0.95–0.99 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5 U_eq(methyl C).

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

	x	y	z	U_iso*/U_eq
C1	0.6168 (4)	0.1527 (2)	0.1730 (5)	0.0375 (10)
C2	0.6242 (4)	0.0886 (2)	0.1758 (5)	0.0401 (10)
N3A	0.4545 (3)	0.11329 (17)	0.2243 (4)	0.0357 (8)
C3	0.5240 (4)	0.0654 (2)	0.2098 (5)	0.0365 (10)
N4A	0.2907 (3)	0.17653 (16)	0.2632 (4)	0.0320 (8)
B4	0.3319 (5)	0.1102 (2)	0.2480 (6)	0.0345 (10)
C5	0.1906 (4)	0.1955 (2)	0.2927 (5)	0.0321 (9)
C6	0.1870 (4)	0.2612 (2)	0.2985 (5)	0.0339 (9)
C7	0.2882 (4)	0.2830 (2)	0.2691 (5)	0.0334 (9)
C7A	0.3531 (4)	0.2300 (2)	0.2478 (5)	0.0332 (9)
C8	0.4593 (4)	0.2254 (2)	0.2161 (5)	0.0378 (10)
H8	0.499101	0.262106	0.202465	0.045*
C8A	0.5107 (4)	0.1680 (2)	0.2034 (5)	0.0344 (9)
F9	0.2522 (2)	0.08108 (12)	0.1056 (3)	0.0419 (6)
F10	0.3365 (2)	0.07568 (12)	0.3926 (3)	0.0463 (7)
C11	0.7237 (4)	0.0497 (2)	0.1543 (6)	0.0447 (11)
H11A	0.765621	0.073310	0.088177	0.054*
H11B	0.690710	0.011961	0.089141	0.054*
C12	0.8112 (4)	0.0313 (2)	0.3255 (6)	0.0462 (12)
H12A	0.845614	0.069219	0.388989	0.055*
H12B	0.768455	0.009078	0.392899	0.055*
C13	0.9092 (4)	−0.0090 (2)	0.3081 (6)	0.0421 (11)
O14	0.9331 (3)	−0.05959 (17)	0.3704 (5)	0.0525 (9)
O15	0.9673 (3)	0.01777 (16)	0.2139 (4)	0.0482 (8)
C16	1.0658 (5)	−0.0171 (3)	0.1959 (7)	0.0571 (14)
H16A	1.112435	0.009131	0.144368	0.086*
H16B	1.036517	−0.053078	0.122765	0.086*
H16C	1.115511	−0.031056	0.308257	0.086*
C17	0.0914 (4)	0.2973 (2)	0.3389 (5)	0.0365 (10)
H17A	0.120908	0.339517	0.374704	0.044*
H17B	0.074036	0.277407	0.436257	0.044*
C18	−0.0232 (4)	0.3022 (2)	0.1904 (5)	0.0343 (9)
H18A	−0.009617	0.328626	0.100521	0.041*
H18B	−0.046000	0.260563	0.141415	0.041*
C19	−0.1220 (4)	0.3287 (2)	0.2435 (5)	0.0372 (10)
O20	−0.1238 (3)	0.33229 (16)	0.3882 (4)	0.0449 (8)
O21	−0.2120 (3)	0.34756 (15)	0.1088 (4)	0.0412 (7)
C22	−0.3121 (4)	0.3733 (3)	0.1478 (7)	0.0512 (13)
H22A	−0.376353	0.380654	0.041848	0.077*
H22B	−0.289255	0.412509	0.208816	0.077*
H22C	−0.338522	0.344308	0.219404	0.077*
C23	0.7046 (5)	0.1981 (2)	0.1491 (7)	0.0506 (12)
H23A	0.663003	0.233367	0.082459	0.076*
H23B	0.753553	0.178161	0.088545	0.076*
H23C	0.754893	0.212549	0.260557	0.076*
C24	0.4960 (4)	0.0000 (2)	0.2359 (6)	0.0420 (11)
H24A	0.523288	−0.026676	0.160100	0.063*
H24B	0.410510	−0.004618	0.210398	0.063*
H24C	0.535739	−0.011763	0.354578	0.063*
C25	0.0994 (4)	0.1511 (2)	0.3080 (6)	0.0399 (10)
H25A	0.045183	0.172126	0.357789	0.060*
H25B	0.137629	0.116608	0.381501	0.060*
H25C	0.055169	0.135340	0.194887	0.060*
C26	0.3262 (4)	0.3483 (2)	0.2625 (5)	0.0377 (10)
H26A	0.339927	0.355885	0.153316	0.057*
H26B	0.399334	0.355734	0.355804	0.057*
H26C	0.264443	0.376188	0.273969	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (2)	0.046 (3)	0.031 (2)	0.002 (2)	0.0166 (19)	−0.0004 (19)
C2	0.043 (2)	0.045 (3)	0.032 (2)	0.006 (2)	0.0103 (19)	−0.0036 (19)
N3A	0.040 (2)	0.037 (2)	0.0308 (18)	0.0052 (16)	0.0126 (16)	0.0006 (15)
C3	0.042 (2)	0.038 (2)	0.031 (2)	0.004 (2)	0.0129 (18)	−0.0005 (18)
N4A	0.0363 (19)	0.0325 (19)	0.0314 (18)	0.0011 (15)	0.0164 (15)	0.0021 (14)
B4	0.042 (3)	0.038 (3)	0.025 (2)	0.003 (2)	0.013 (2)	0.0021 (19)
C5	0.035 (2)	0.039 (2)	0.0240 (19)	0.0021 (18)	0.0110 (17)	−0.0012 (16)
C6	0.038 (2)	0.041 (2)	0.0244 (19)	0.0009 (19)	0.0122 (17)	−0.0015 (17)
C7	0.038 (2)	0.037 (2)	0.025 (2)	0.0002 (18)	0.0088 (17)	−0.0012 (16)
C7A	0.039 (2)	0.036 (2)	0.025 (2)	0.0024 (19)	0.0123 (17)	−0.0001 (17)
C8	0.042 (2)	0.041 (3)	0.033 (2)	0.004 (2)	0.0153 (19)	0.0032 (19)
C8A	0.039 (2)	0.034 (2)	0.034 (2)	0.0003 (19)	0.0155 (18)	−0.0020 (17)
F9	0.0437 (14)	0.0432 (15)	0.0382 (14)	−0.0020 (12)	0.0123 (11)	−0.0047 (11)
F10	0.0596 (17)	0.0445 (16)	0.0405 (14)	0.0089 (13)	0.0238 (13)	0.0098 (12)
C11	0.044 (3)	0.050 (3)	0.041 (3)	0.005 (2)	0.014 (2)	−0.009 (2)
C12	0.045 (3)	0.056 (3)	0.038 (2)	0.009 (2)	0.014 (2)	−0.003 (2)
C13	0.036 (2)	0.050 (3)	0.038 (2)	−0.002 (2)	0.0085 (19)	0.002 (2)
O14	0.053 (2)	0.049 (2)	0.053 (2)	0.0036 (17)	0.0130 (17)	0.0062 (17)
O15	0.0476 (19)	0.051 (2)	0.052 (2)	0.0070 (16)	0.0231 (16)	0.0032 (16)
C16	0.053 (3)	0.067 (4)	0.057 (3)	0.012 (3)	0.025 (3)	0.002 (3)
C17	0.041 (2)	0.044 (3)	0.028 (2)	0.005 (2)	0.0146 (18)	−0.0009 (18)
C18	0.037 (2)	0.040 (2)	0.027 (2)	0.0010 (19)	0.0126 (17)	−0.0018 (17)
C19	0.043 (2)	0.039 (2)	0.033 (2)	−0.001 (2)	0.0158 (19)	−0.0009 (18)
O20	0.0460 (18)	0.058 (2)	0.0358 (17)	0.0070 (16)	0.0203 (14)	0.0003 (15)
O21	0.0360 (16)	0.051 (2)	0.0364 (16)	0.0061 (15)	0.0112 (13)	0.0013 (14)
C22	0.037 (2)	0.066 (3)	0.054 (3)	0.011 (2)	0.019 (2)	0.004 (3)
C23	0.050 (3)	0.053 (3)	0.055 (3)	−0.003 (2)	0.025 (2)	−0.003 (2)
C24	0.047 (3)	0.040 (3)	0.039 (2)	0.004 (2)	0.012 (2)	−0.001 (2)
C25	0.042 (2)	0.048 (3)	0.036 (2)	0.000 (2)	0.019 (2)	0.0010 (19)
C26	0.044 (2)	0.037 (2)	0.033 (2)	0.000 (2)	0.0123 (19)	−0.0003 (18)

Geometric parameters (Å, º) top

C1—C2	1.389 (6)	C13—O15	1.326 (5)
C1—C8A	1.405 (6)	O15—C16	1.443 (6)
C1—C23	1.494 (6)	C16—H16A	0.9800
C2—C3	1.404 (6)	C16—H16B	0.9800
C2—C11	1.510 (6)	C16—H16C	0.9800
N3A—C3	1.356 (5)	C17—C18	1.528 (6)
N3A—C8A	1.396 (5)	C17—H17A	0.9900
N3A—B4	1.537 (6)	C17—H17B	0.9900
C3—C24	1.483 (6)	C18—C19	1.496 (6)
N4A—C5	1.355 (5)	C18—H18A	0.9900
N4A—C7A	1.403 (5)	C18—H18B	0.9900
N4A—B4	1.535 (6)	C19—O20	1.205 (5)
B4—F10	1.395 (5)	C19—O21	1.345 (5)
B4—F9	1.409 (5)	O21—C22	1.442 (5)
C5—C6	1.424 (6)	C22—H22A	0.9800
C5—C25	1.486 (6)	C22—H22B	0.9800
C6—C7	1.386 (6)	C22—H22C	0.9800
C6—C17	1.504 (6)	C23—H23A	0.9800
C7—C7A	1.424 (6)	C23—H23B	0.9800
C7—C26	1.490 (6)	C23—H23C	0.9800
C7A—C8	1.375 (6)	C24—H24A	0.9800
C8—C8A	1.403 (6)	C24—H24B	0.9800
C8—H8	0.9500	C24—H24C	0.9800
C11—C12	1.525 (7)	C25—H25A	0.9800
C11—H11A	0.9900	C25—H25B	0.9800
C11—H11B	0.9900	C25—H25C	0.9800
C12—C13	1.501 (6)	C26—H26A	0.9800
C12—H12A	0.9900	C26—H26B	0.9800
C12—H12B	0.9900	C26—H26C	0.9800
C13—O14	1.205 (6)

C2—C1—C8A	106.8 (4)	C13—O15—C16	115.1 (4)
C2—C1—C23	127.9 (4)	O15—C16—H16A	109.5
C8A—C1—C23	125.3 (4)	O15—C16—H16B	109.5
C1—C2—C3	107.8 (4)	H16A—C16—H16B	109.5
C1—C2—C11	127.0 (4)	O15—C16—H16C	109.5
C3—C2—C11	125.1 (4)	H16A—C16—H16C	109.5
C3—N3A—C8A	107.8 (3)	H16B—C16—H16C	109.5
C3—N3A—B4	127.6 (4)	C6—C17—C18	114.1 (3)
C8A—N3A—B4	124.4 (4)	C6—C17—H17A	108.7
N3A—C3—C2	109.1 (4)	C18—C17—H17A	108.7
N3A—C3—C24	122.9 (4)	C6—C17—H17B	108.7
C2—C3—C24	127.9 (4)	C18—C17—H17B	108.7
C5—N4A—C7A	106.8 (3)	H17A—C17—H17B	107.6
C5—N4A—B4	128.4 (4)	C19—C18—C17	112.3 (3)
C7A—N4A—B4	124.8 (3)	C19—C18—H18A	109.1
F10—B4—F9	108.2 (4)	C17—C18—H18A	109.1
F10—B4—N4A	111.0 (3)	C19—C18—H18B	109.1
F9—B4—N4A	109.7 (4)	C17—C18—H18B	109.1
F10—B4—N3A	110.4 (4)	H18A—C18—H18B	107.9
F9—B4—N3A	109.4 (3)	O20—C19—O21	123.0 (4)
N4A—B4—N3A	108.2 (4)	O20—C19—C18	125.2 (4)
N4A—C5—C6	110.2 (4)	O21—C19—C18	111.8 (3)
N4A—C5—C25	122.0 (4)	C19—O21—C22	115.7 (3)
C6—C5—C25	127.7 (4)	O21—C22—H22A	109.5
C7—C6—C5	107.2 (4)	O21—C22—H22B	109.5
C7—C6—C17	128.7 (4)	H22A—C22—H22B	109.5
C5—C6—C17	123.9 (4)	O21—C22—H22C	109.5
C6—C7—C7A	106.6 (4)	H22A—C22—H22C	109.5
C6—C7—C26	128.3 (4)	H22B—C22—H22C	109.5
C7A—C7—C26	125.0 (4)	C1—C23—H23A	109.5
C8—C7A—N4A	120.2 (4)	C1—C23—H23B	109.5
C8—C7A—C7	130.7 (4)	H23A—C23—H23B	109.5
N4A—C7A—C7	109.1 (3)	C1—C23—H23C	109.5
C7A—C8—C8A	121.9 (4)	H23A—C23—H23C	109.5
C7A—C8—H8	119.0	H23B—C23—H23C	109.5
C8A—C8—H8	119.0	C3—C24—H24A	109.5
N3A—C8A—C8	120.2 (4)	C3—C24—H24B	109.5
N3A—C8A—C1	108.5 (4)	H24A—C24—H24B	109.5
C8—C8A—C1	131.3 (4)	C3—C24—H24C	109.5
C2—C11—C12	111.8 (4)	H24A—C24—H24C	109.5
C2—C11—H11A	109.3	H24B—C24—H24C	109.5
C12—C11—H11A	109.3	C5—C25—H25A	109.5
C2—C11—H11B	109.3	C5—C25—H25B	109.5
C12—C11—H11B	109.3	H25A—C25—H25B	109.5
H11A—C11—H11B	107.9	C5—C25—H25C	109.5
C13—C12—C11	112.9 (4)	H25A—C25—H25C	109.5
C13—C12—H12A	109.0	H25B—C25—H25C	109.5
C11—C12—H12A	109.0	C7—C26—H26A	109.5
C13—C12—H12B	109.0	C7—C26—H26B	109.5
C11—C12—H12B	109.0	H26A—C26—H26B	109.5
H12A—C12—H12B	107.8	C7—C26—H26C	109.5
O14—C13—O15	123.4 (4)	H26A—C26—H26C	109.5
O14—C13—C12	125.0 (4)	H26B—C26—H26C	109.5
O15—C13—C12	111.6 (4)

C8A—C1—C2—C3	−0.8 (5)	C17—C6—C7—C26	−2.9 (7)
C23—C1—C2—C3	177.2 (4)	C5—N4A—C7A—C8	−179.6 (4)
C8A—C1—C2—C11	−178.2 (4)	B4—N4A—C7A—C8	0.2 (6)
C23—C1—C2—C11	−0.2 (8)	C5—N4A—C7A—C7	0.1 (4)
C8A—N3A—C3—C2	−1.3 (5)	B4—N4A—C7A—C7	180.0 (4)
B4—N3A—C3—C2	175.1 (4)	C6—C7—C7A—C8	−179.9 (4)
C8A—N3A—C3—C24	176.0 (4)	C26—C7—C7A—C8	−0.7 (7)
B4—N3A—C3—C24	−7.6 (7)	C6—C7—C7A—N4A	0.4 (4)
C1—C2—C3—N3A	1.3 (5)	C26—C7—C7A—N4A	179.6 (4)
C11—C2—C3—N3A	178.8 (4)	N4A—C7A—C8—C8A	−2.0 (6)
C1—C2—C3—C24	−175.8 (4)	C7—C7A—C8—C8A	178.3 (4)
C11—C2—C3—C24	1.7 (7)	C3—N3A—C8A—C8	−178.6 (4)
C5—N4A—B4—F10	−55.6 (6)	B4—N3A—C8A—C8	4.9 (6)
C7A—N4A—B4—F10	124.6 (4)	C3—N3A—C8A—C1	0.8 (5)
C5—N4A—B4—F9	63.9 (5)	B4—N3A—C8A—C1	−175.8 (4)
C7A—N4A—B4—F9	−116.0 (4)	C7A—C8—C8A—N3A	−0.5 (6)
C5—N4A—B4—N3A	−176.9 (4)	C7A—C8—C8A—C1	−179.7 (4)
C7A—N4A—B4—N3A	3.3 (5)	C2—C1—C8A—N3A	0.0 (5)
C3—N3A—B4—F10	56.7 (6)	C23—C1—C8A—N3A	−178.1 (4)
C8A—N3A—B4—F10	−127.4 (4)	C2—C1—C8A—C8	179.3 (5)
C3—N3A—B4—F9	−62.3 (5)	C23—C1—C8A—C8	1.2 (8)
C8A—N3A—B4—F9	113.6 (4)	C1—C2—C11—C12	95.7 (6)
C3—N3A—B4—N4A	178.3 (4)	C3—C2—C11—C12	−81.3 (6)
C8A—N3A—B4—N4A	−5.8 (5)	C2—C11—C12—C13	178.2 (4)
C7A—N4A—C5—C6	−0.6 (5)	C11—C12—C13—O14	−123.1 (5)
B4—N4A—C5—C6	179.6 (4)	C11—C12—C13—O15	56.6 (6)
C7A—N4A—C5—C25	177.1 (4)	O14—C13—O15—C16	−2.4 (7)
B4—N4A—C5—C25	−2.8 (6)	C12—C13—O15—C16	177.9 (4)
N4A—C5—C6—C7	0.8 (5)	C7—C6—C17—C18	105.4 (5)
C25—C5—C6—C7	−176.6 (4)	C5—C6—C17—C18	−78.1 (5)
N4A—C5—C6—C17	−176.4 (3)	C6—C17—C18—C19	170.2 (4)
C25—C5—C6—C17	6.2 (7)	C17—C18—C19—O20	−17.2 (6)
C5—C6—C7—C7A	−0.7 (5)	C17—C18—C19—O21	164.1 (4)
C17—C6—C7—C7A	176.3 (4)	O20—C19—O21—C22	0.7 (7)
C5—C6—C7—C26	−179.8 (4)	C18—C19—O21—C22	179.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···F9ⁱ	0.98	2.37	3.324 (7)	163
C18—H18A···O14ⁱⁱ	0.99	2.57	3.268 (6)	128
C23—H23B···O20ⁱⁱⁱ	0.98	2.54	3.470 (7)	158

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

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