N-(10-Bromo­anthracen-9-yl­methyl)-N-[2-(5,5-di­methyl-1,3,2-dioxaborinan-2-yl)­benzyl]­methyl­amine at 240 K

Barkhuizen, D.A.; Howie, R.A.; Maguire, G.E.M.; Rademeyer, M.

doi:10.1107/S1600536804005410

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 4| April 2004| Pages o571-o573

https://doi.org/10.1107/S1600536804005410

N-(10-Bromoanthracen-9-ylmethyl)-N-[2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzyl]methylamine at 240 K

David A. Barkhuizen,^a R. Alan Howie,^b ^* Glenn E. M. Maguire ^a and Melanie Rademeyer ^a

^aSchool of Pure and Applied Chemistry, University of Kwazulu–Natal, Durban 4041, South Africa, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: r.a.howie@abdn.ac.uk

(Received 2 March 2004; accepted 8 March 2004; online 24 March 2004)

Features of the structure of the title compound, C₂₈H₂₉BBrNO₂, are the planar coordination of B and the intramolecular B⋯N contact distance of 3.204 (3) Å. The molecules form layers parallel to (010), with the creation of π–π and C—H⋯π contacts.

Comment

The synthesis and structure determination of the title compound, (I), is part of a continuing study, following on from the work of James et al. (1994 ), of compounds of potential value for use as sensors for sugar-like species. The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. Bond lengths in the aryl fragments are in the ranges 1.351 (3)–1.445 (2) Å and 1.364 (3)–1.403 (3) Å for the bromoanthracene (C1–C14) and benzene ring (C18–C23) moieties, respectively. The C7—Br1 bond length [1.909 (2) Å] is, like all of the bond lengths found in this structure, as expected for a molecule of this kind. Particularly significant, however, is the intramolecular B1⋯N1 distance of 3.204 (3) Å. The dihedral angle between the least-squares planes (unit weights applied to the constituent atoms) of the anthracene and benzene ring groups as defined above is 69.64 (8)°. The relevant torsion angles in Table 1 are clearly compatible with the description of the conformation of the six-membered dioxaborinane ring as an envelope, with atom C25 at the point of the flap and with puckering parameters (Cremer & Pople, 1975 ) Q(2), Q(3) and φ(2) of 0.384 (2) Å, −0.273 (2) Å and 359.3 (3)°, respectively [overall Q = 0.471 (2) Å, θ = 125.5 (2)° and φ = φ(2) for the ring atoms in the order B1—O1—C24—C25—C28—O2]. The only axial non-H-atom substituent is atom C26.

In the unit cell, the molecules form layers in such a way as to induce two kinds of intermolecular contacts between pairs of centrosymmetrically related molecules. This situation is illustrated in Fig. 2, where these interactions are shown as dashed lines. The first is a π–π interaction between anthracene fragments, which is most conveniently assessed in terms of the overlap of the rings of the form C1/C6–C8/C13/C14. These rings are related to one another (symmetry code: 2 − x, −y, 1 − z) by crystallographic centres of symmetry and their least-squares planes are then, by definition, precisely parallel to one another. In this circumstance, the overlap between the rings can be completely specified in terms of the distance between the centroids [3.950 (1) Å] and the perpendicular distance between the overlapping rings [3.483 (1) Å]. These values can be treated as two sides of a right-angled triangle of which the third side [1.863 (1) Å] is the lateral displacement or slippage of the overlapping rings in a direction parallel to their least-squares planes. The overlap of the anthracene fragments is shown more fully in Fig. 3. The second intermolecular contact in the layer of molecules is of the C—H⋯π type and involves atoms C28 and H28A and the benzene ring, defined by C18–23, with centroid Cg (symmetry code: 1 − x, y, $[{1 \over 2}]$ − z). This interaction is characterized by C—H, H⋯Cg, H_perp (the perpendicular distance of H28A from the plane of the benzene ring) and C⋯Cg distances of 0.98, 3.32, 3.19 and 4.224 (3) Å, respectively. The C28—H28A⋯Cg angle and the angle at H28A between H28A⋯Cg and H_perp are 154 and 16°, respectively.

Figure 1
The molecular structure of (I

), showing the labelling scheme. Non-H atoms are shown as 50% probability displacement ellipsoids and H atoms are shown as small spheres of arbitrary radii.

Figure 2
Part of a layer, parallel to (010), of molecules of (I

). Intermolecular C—H⋯π and π–π contacts as explained in the text are denoted by dashed lines. The representation is otherwise the same as in Fig. 1

, except that only selected atoms are labelled and H atoms not used in forming intermolecular contacts have been omitted. [Symmetry codes: (i) 2 − x, −y, 1 − z; (ii) 2 − x, y, $[{1 \over 2}]$ − z; (iii) x, −y, z − $[1\over 2]$ ; (iv) x − 1, y, z; (v) 1 − x, −y, 1 − z; (vi) 1 − x, y, $[{1 \over 2}]$ − z; (vii) x − 1, −y, z − $[1\over2]$ .]

Figure 3
A pair of incomplete molecules of (I

), displaying the overlap of the anthracene fragments. Non-H atoms are shown as 50% probability displacement ellipsoids and H atoms have been omitted for clarity. Selected atoms are labelled. The dashed line joins the ring centroids mentioned in the text. [Symmetry code: (i) 2 − x, −y, 1 − z.]

Experimental

Compound (I) was synthesized according to the procedure of James et al. (1995 ) but with 10-bromo-9-bromomethylanthracene as starting material. The product was recrystallized from methanol in a refrigerator at 283 K (m.p. 340–342 K). ¹H NMR (300 MHz, CDCl₃): δ 7.29–8.56 (m, 12H, ArH), 4.35 (s, 2H, ArCH₂), 3.92 (s, 2H, ArCH₂), 3.54 (s, 4H, OCH₂), 2.18 (s, 3H, NCH₃), 0.89 [s, 6H, C(CH₃)₂].

Crystal data

C₂₈H₂₉BBrNO₂
M_r = 502.24
Monoclinic, C2/c
a = 12.854 (7) Å
b = 14.457 (9) Å
c = 26.686 (11) Å
β = 100.06 (4)°
V = 4883 (5) Å³
Z = 8
D_x = 1.366 Mg m⁻³
Mo Kα radiation
Cell parameters from 22 217 reflections
θ = 4.3–31.9°
μ = 1.71 mm⁻¹
T = 240 (2) K
Block, yellow
0.40 × 0.40 × 0.35 mm

Data collection

Oxford Diffraction Excalibur2 CCD area-detector diffractometer
ω/2θ scans
Absorption correction: multi-scan (Blessing, 1995 , 1997 ) T_min = 0.907, T_max = 1.000
22 217 measured reflections
7799 independent reflections
3964 reflections with I > 2σ(I)
R_int = 0.038
θ_max = 31.9°
h = −17 → 18
k = −20 → 18
l = −39 → 39

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.085
S = 0.87
7799 reflections
301 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0341P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C7—Br1	1.909 (2)
C15—N1	1.465 (2)
N1—C16	1.454 (2)
N1—C17	1.465 (2)
C23—B1	1.576 (3)
B1—O1	1.353 (3)
B1—O2	1.357 (3)
O1—C24	1.438 (2)
C24—C25	1.515 (3)
C25—C28	1.511 (3)
C28—O2	1.440 (3)

C16—N1—C15	111.55 (15)
C16—N1—C17	109.82 (14)
C15—N1—C17	109.82 (14)
O1—B1—C23	121.02 (19)
O2—B1—C23	115.7 (2)
O1—B1—O2	123.2 (2)
B1—O1—C24	119.76 (17)
O1—C24—C25	112.36 (17)
C28—C25—C24	107.60 (19)
O2—C28—C25	112.76 (18)
B1—O2—C28	119.39 (18)

O2—B1—O1—C24	−0.8 (3)
B1—O1—C24—C25	−27.9 (3)
O1—C24—C25—C28	52.9 (3)
C24—C25—C28—O2	−52.7 (3)
C25—C28—O2—B1	27.3 (3)
O1—B1—O2—C28	1.2 (3)
C23—B1—O1—C24	−178.20 (18)
C23—B1—O2—C28	178.75 (18)
O1—C24—C25—C26	−68.2 (2)
O1—C24—C25—C27	170.64 (19)
C26—C25—C28—O2	67.5 (3)
C27—C25—C28—O2	−170.9 (2)

In the final stages of refinement, H atoms were placed in calculated positions, with C—H = 0.94, 0.97 and 0.98 Å for aryl, methyl and methylene H atoms, respectively, and refined using a riding model, with U_iso(H) values set at 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Data collection: CrysAlisCCD (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlisCCD and CrysAlisRED. Versions 1.170. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlisCCD; data reduction: CrysAlisRED (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlisCCD and CrysAlisRED. Versions 1.170. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804005410/su6083sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804005410/su6083Isup2.hkl

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

N-(10-Bromoanthracen-9-ylmethyl)-N-[2-(5,5-dimethyl-1,3,2-dioxaborinan-2- yl)benzyl]methylamine top

Crystal data top

C₂₈H₂₉BBrNO₂	F(000) = 2080
M_r = 502.24	D_x = 1.366 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.854 (7) Å	Cell parameters from 22217 reflections
b = 14.457 (9) Å	θ = 4.3–31.9°
c = 26.686 (11) Å	µ = 1.71 mm⁻¹
β = 100.06 (4)°	T = 240 K
V = 4883 (5) Å³	Block, yellow
Z = 8	0.40 × 0.40 × 0.35 mm

Data collection top

Oxford Instruments Excalibur2 CCD area-detector diffractometer	7799 independent reflections
Radiation source: fine-focus sealed tube	3964 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω/2θ scans	θ_max = 31.9°, θ_min = 4.3°
Absorption correction: multi-scan (Blessing, 1995, 1997)	h = −17→18
T_min = 0.907, T_max = 1.000	k = −20→18
22217 measured reflections	l = −39→39

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: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 0.87	w = 1/[σ²(F_o²) + (0.0341P)²] where P = (F_o² + 2F_c²)/3
7799 reflections	(Δ/σ)_max = 0.001
301 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	1.00768 (13)	0.11827 (11)	0.47589 (7)	0.0263 (4)
C2	0.98551 (15)	0.17985 (13)	0.51471 (7)	0.0357 (5)
H2	0.9147	0.1937	0.5163	0.043*
C3	1.06275 (16)	0.21884 (14)	0.54909 (8)	0.0410 (5)
H3	1.0451	0.2588	0.5741	0.049*
C4	1.16931 (16)	0.19984 (14)	0.54764 (8)	0.0406 (5)
H4	1.2225	0.2268	0.5719	0.049*
C5	1.19588 (14)	0.14315 (12)	0.51166 (7)	0.0335 (4)
H5	1.2676	0.1314	0.5112	0.040*
C6	1.11789 (13)	0.10103 (12)	0.47450 (7)	0.0275 (4)
C7	1.14230 (14)	0.04195 (12)	0.43666 (7)	0.0300 (4)
C8	1.06619 (14)	−0.00107 (12)	0.40060 (7)	0.0298 (4)
C9	1.09059 (16)	−0.06173 (13)	0.36229 (7)	0.0390 (5)
H9	1.1617	−0.0740	0.3606	0.047*
C10	1.01365 (18)	−0.10229 (14)	0.32809 (8)	0.0481 (6)
H10	1.0317	−0.1420	0.3031	0.058*
C11	0.90665 (17)	−0.08475 (14)	0.33011 (8)	0.0459 (5)
H11	0.8536	−0.1126	0.3061	0.055*
C12	0.87942 (15)	−0.02842 (12)	0.36609 (7)	0.0361 (5)
H12	0.8075	−0.0185	0.3669	0.043*
C13	0.95661 (13)	0.01626 (12)	0.40287 (7)	0.0276 (4)
C14	0.92829 (13)	0.07521 (12)	0.44044 (7)	0.0269 (4)
C15	0.81203 (13)	0.08650 (12)	0.44265 (7)	0.0296 (4)
H15A	0.7797	0.0251	0.4423	0.035*
H15B	0.8052	0.1163	0.4749	0.035*
N1	0.75375 (11)	0.14110 (10)	0.40070 (6)	0.0287 (3)
C16	0.78962 (16)	0.23665 (13)	0.40270 (9)	0.0469 (5)
H16A	0.7725	0.2663	0.4328	0.070*
H16B	0.7548	0.2692	0.3726	0.070*
H16C	0.8655	0.2382	0.4040	0.070*
C17	0.64047 (13)	0.13793 (13)	0.40230 (7)	0.0362 (5)
H17A	0.6037	0.1839	0.3786	0.043*
H17B	0.6292	0.1542	0.4366	0.043*
C18	0.59414 (13)	0.04339 (14)	0.38841 (7)	0.0357 (5)
C19	0.55765 (15)	−0.00943 (15)	0.42532 (8)	0.0448 (5)
H19	0.5571	0.0161	0.4577	0.054*
C20	0.52202 (16)	−0.09926 (17)	0.41514 (10)	0.0568 (6)
H20	0.4977	−0.1342	0.4405	0.068*
C21	0.52252 (17)	−0.13653 (17)	0.36825 (10)	0.0586 (6)
H21	0.4991	−0.1976	0.3613	0.070*
C22	0.55737 (16)	−0.08461 (16)	0.33091 (9)	0.0496 (6)
H22	0.5569	−0.1111	0.2987	0.060*
C23	0.59334 (14)	0.00611 (13)	0.33980 (8)	0.0365 (5)
B1	0.63288 (17)	0.05875 (18)	0.29493 (9)	0.0407 (6)
O1	0.61759 (11)	0.15084 (10)	0.28833 (5)	0.0502 (4)
C24	0.65182 (19)	0.19649 (17)	0.24618 (9)	0.0573 (6)
H24A	0.6718	0.2603	0.2559	0.069*
H24B	0.5929	0.1987	0.2174	0.069*
C25	0.74475 (17)	0.14806 (15)	0.22963 (8)	0.0474 (5)
C26	0.84277 (18)	0.15812 (18)	0.27099 (10)	0.0655 (7)
H26A	0.8282	0.1327	0.3027	0.098*
H26B	0.8608	0.2231	0.2757	0.098*
H26C	0.9014	0.1250	0.2608	0.098*
C27	0.7649 (2)	0.19040 (18)	0.17960 (9)	0.0727 (8)
H27A	0.8238	0.1589	0.1687	0.109*
H27B	0.7815	0.2555	0.1847	0.109*
H27C	0.7022	0.1836	0.1537	0.109*
C28	0.7151 (2)	0.04756 (17)	0.22043 (9)	0.0603 (7)
H28A	0.6594	0.0429	0.1904	0.072*
H28B	0.7767	0.0134	0.2133	0.072*
O2	0.67864 (12)	0.00534 (10)	0.26306 (5)	0.0508 (4)
Br1	1.287387 (16)	0.017499 (16)	0.434454 (9)	0.04864 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0281 (9)	0.0231 (9)	0.0281 (10)	0.0037 (7)	0.0059 (8)	0.0033 (8)
C2	0.0321 (11)	0.0366 (11)	0.0394 (12)	0.0041 (8)	0.0089 (9)	−0.0025 (9)
C3	0.0439 (12)	0.0423 (13)	0.0368 (12)	0.0033 (10)	0.0065 (10)	−0.0107 (10)
C4	0.0386 (12)	0.0405 (12)	0.0392 (12)	−0.0068 (9)	−0.0029 (10)	−0.0052 (10)
C5	0.0260 (10)	0.0350 (11)	0.0388 (11)	−0.0007 (8)	0.0040 (8)	0.0019 (9)
C6	0.0277 (9)	0.0282 (10)	0.0269 (10)	−0.0003 (7)	0.0052 (8)	0.0041 (8)
C7	0.0267 (9)	0.0341 (11)	0.0302 (10)	0.0052 (8)	0.0079 (8)	0.0051 (8)
C8	0.0315 (9)	0.0300 (11)	0.0278 (10)	0.0047 (8)	0.0050 (8)	0.0026 (8)
C9	0.0392 (11)	0.0408 (12)	0.0379 (12)	0.0097 (9)	0.0095 (10)	−0.0029 (10)
C10	0.0582 (15)	0.0458 (13)	0.0407 (13)	0.0101 (11)	0.0095 (11)	−0.0146 (11)
C11	0.0465 (13)	0.0413 (13)	0.0448 (13)	0.0028 (10)	−0.0061 (10)	−0.0121 (10)
C12	0.0324 (10)	0.0315 (11)	0.0419 (12)	0.0017 (8)	0.0000 (9)	−0.0038 (9)
C13	0.0297 (9)	0.0234 (9)	0.0291 (9)	0.0022 (7)	0.0036 (8)	0.0024 (8)
C14	0.0266 (9)	0.0250 (10)	0.0296 (10)	0.0037 (7)	0.0059 (8)	0.0053 (8)
C15	0.0279 (10)	0.0293 (10)	0.0318 (11)	0.0005 (7)	0.0059 (8)	0.0016 (8)
N1	0.0234 (8)	0.0270 (8)	0.0354 (9)	0.0036 (6)	0.0045 (7)	0.0037 (7)
C16	0.0471 (13)	0.0310 (12)	0.0624 (15)	0.0014 (9)	0.0094 (11)	0.0092 (11)
C17	0.0279 (10)	0.0445 (12)	0.0365 (11)	0.0114 (9)	0.0068 (8)	0.0040 (9)
C18	0.0179 (9)	0.0486 (13)	0.0403 (12)	0.0040 (8)	0.0044 (8)	0.0051 (10)
C19	0.0263 (10)	0.0697 (16)	0.0393 (12)	−0.0052 (10)	0.0080 (9)	0.0008 (11)
C20	0.0372 (12)	0.0731 (17)	0.0614 (16)	−0.0174 (12)	0.0126 (11)	0.0146 (14)
C21	0.0500 (14)	0.0575 (15)	0.0691 (17)	−0.0245 (12)	0.0124 (13)	−0.0047 (14)
C22	0.0369 (12)	0.0643 (16)	0.0472 (14)	−0.0099 (10)	0.0060 (10)	−0.0023 (12)
C23	0.0202 (9)	0.0476 (13)	0.0401 (11)	−0.0008 (8)	0.0014 (8)	0.0022 (10)
B1	0.0285 (12)	0.0543 (16)	0.0375 (14)	0.0034 (11)	0.0011 (10)	0.0008 (12)
O1	0.0523 (9)	0.0562 (10)	0.0457 (9)	0.0183 (7)	0.0185 (7)	0.0183 (8)
C24	0.0596 (15)	0.0642 (16)	0.0494 (14)	0.0135 (12)	0.0133 (12)	0.0249 (12)
C25	0.0501 (13)	0.0565 (15)	0.0372 (12)	0.0007 (11)	0.0120 (10)	0.0097 (11)
C26	0.0503 (15)	0.0789 (18)	0.0679 (17)	−0.0034 (13)	0.0116 (13)	0.0139 (14)
C27	0.085 (2)	0.0823 (19)	0.0568 (17)	−0.0016 (15)	0.0291 (15)	0.0153 (14)
C28	0.0704 (17)	0.0725 (18)	0.0427 (14)	−0.0069 (13)	0.0232 (12)	0.0006 (12)
O2	0.0604 (10)	0.0521 (10)	0.0440 (9)	−0.0048 (7)	0.0207 (8)	−0.0002 (7)
Br1	0.02980 (11)	0.06577 (16)	0.05168 (14)	0.00946 (10)	0.01076 (9)	−0.00139 (12)

Geometric parameters (Å, º) top

C1—C14	1.410 (2)	C16—H16C	0.9700
C1—C2	1.432 (3)	C17—C18	1.511 (3)
C1—C6	1.445 (2)	C17—H17A	0.9800
C2—C3	1.352 (3)	C17—H17B	0.9800
C2—H2	0.9400	C18—C19	1.391 (3)
C3—C4	1.404 (3)	C18—C23	1.403 (3)
C3—H3	0.9400	C19—C20	1.388 (3)
C4—C5	1.351 (3)	C19—H19	0.9400
C4—H4	0.9400	C20—C21	1.364 (3)
C5—C6	1.418 (2)	C20—H20	0.9400
C5—H5	0.9400	C21—C22	1.383 (3)
C6—C7	1.400 (2)	C21—H21	0.9400
C7—C8	1.393 (3)	C22—C23	1.397 (3)
C7—Br1	1.909 (2)	C22—H22	0.9400
C8—C9	1.423 (3)	C23—B1	1.576 (3)
C8—C13	1.442 (3)	B1—O1	1.353 (3)
C9—C10	1.356 (3)	B1—O2	1.357 (3)
C9—H9	0.9400	O1—C24	1.438 (2)
C10—C11	1.409 (3)	C24—C25	1.515 (3)
C10—H10	0.9400	C24—H24A	0.9800
C11—C12	1.351 (3)	C24—H24B	0.9800
C11—H11	0.9400	C25—C28	1.511 (3)
C12—C13	1.423 (3)	C25—C26	1.530 (3)
C12—H12	0.9400	C25—C27	1.532 (3)
C13—C14	1.411 (2)	C26—H26A	0.9700
C14—C15	1.515 (2)	C26—H26B	0.9700
C15—N1	1.465 (2)	C26—H26C	0.9700
C15—H15A	0.9800	C27—H27A	0.9700
C15—H15B	0.9800	C27—H27B	0.9700
N1—C16	1.454 (2)	C27—H27C	0.9700
N1—C17	1.465 (2)	C28—O2	1.440 (3)
C16—H16A	0.9700	C28—H28A	0.9800
C16—H16B	0.9700	C28—H28B	0.9800

C14—C1—C2	123.22 (16)	N1—C17—H17A	109.2
C14—C1—C6	120.31 (16)	C18—C17—H17A	109.2
C2—C1—C6	116.47 (16)	N1—C17—H17B	109.2
C3—C2—C1	122.34 (18)	C18—C17—H17B	109.2
C3—C2—H2	118.8	H17A—C17—H17B	107.9
C1—C2—H2	118.8	C19—C18—C23	119.66 (19)
C2—C3—C4	120.27 (19)	C19—C18—C17	119.34 (18)
C2—C3—H3	119.9	C23—C18—C17	120.88 (17)
C4—C3—H3	119.9	C20—C19—C18	121.0 (2)
C5—C4—C3	120.49 (18)	C20—C19—H19	119.5
C5—C4—H4	119.8	C18—C19—H19	119.5
C3—C4—H4	119.8	C21—C20—C19	119.7 (2)
C4—C5—C6	121.45 (17)	C21—C20—H20	120.2
C4—C5—H5	119.3	C19—C20—H20	120.2
C6—C5—H5	119.3	C20—C21—C22	120.1 (2)
C7—C6—C5	123.12 (16)	C20—C21—H21	120.0
C7—C6—C1	117.90 (16)	C22—C21—H21	120.0
C5—C6—C1	118.97 (16)	C21—C22—C23	121.8 (2)
C8—C7—C6	123.51 (16)	C21—C22—H22	119.1
C8—C7—Br1	117.90 (13)	C23—C22—H22	119.1
C6—C7—Br1	118.59 (14)	C22—C23—C18	117.81 (18)
C7—C8—C9	123.71 (17)	C22—C23—B1	117.73 (19)
C7—C8—C13	117.82 (16)	C18—C23—B1	124.45 (18)
C9—C8—C13	118.46 (17)	O1—B1—C23	121.02 (19)
C10—C9—C8	121.57 (19)	O2—B1—C23	115.7 (2)
C10—C9—H9	119.2	O1—B1—O2	123.2 (2)
C8—C9—H9	119.2	B1—O1—C24	119.76 (17)
C9—C10—C11	119.89 (19)	O1—C24—C25	112.36 (17)
C9—C10—H10	120.1	O1—C24—H24A	109.1
C11—C10—H10	120.1	C25—C24—H24A	109.1
C12—C11—C10	120.77 (19)	O1—C24—H24B	109.1
C12—C11—H11	119.6	C25—C24—H24B	109.1
C10—C11—H11	119.6	H24A—C24—H24B	107.9
C11—C12—C13	121.86 (18)	C28—C25—C24	107.60 (19)
C11—C12—H12	119.1	C28—C25—C26	111.17 (19)
C13—C12—H12	119.1	C24—C25—C26	109.73 (19)
C14—C13—C12	121.93 (16)	C28—C25—C27	108.59 (19)
C14—C13—C8	120.64 (16)	C24—C25—C27	109.36 (19)
C12—C13—C8	117.43 (16)	C26—C25—C27	110.3 (2)
C1—C14—C13	119.82 (15)	C25—C26—H26A	109.5
C1—C14—C15	122.00 (15)	C25—C26—H26B	109.5
C13—C14—C15	118.12 (16)	H26A—C26—H26B	109.5
N1—C15—C14	113.88 (14)	C25—C26—H26C	109.5
N1—C15—H15A	108.8	H26A—C26—H26C	109.5
C14—C15—H15A	108.8	H26B—C26—H26C	109.5
N1—C15—H15B	108.8	C25—C27—H27A	109.5
C14—C15—H15B	108.8	C25—C27—H27B	109.5
H15A—C15—H15B	107.7	H27A—C27—H27B	109.5
C16—N1—C15	111.55 (15)	C25—C27—H27C	109.5
C16—N1—C17	109.82 (14)	H27A—C27—H27C	109.5
C15—N1—C17	109.82 (14)	H27B—C27—H27C	109.5
N1—C16—H16A	109.5	O2—C28—C25	112.76 (18)
N1—C16—H16B	109.5	O2—C28—H28A	109.0
H16A—C16—H16B	109.5	C25—C28—H28A	109.0
N1—C16—H16C	109.5	O2—C28—H28B	109.0
H16A—C16—H16C	109.5	C25—C28—H28B	109.0
H16B—C16—H16C	109.5	H28A—C28—H28B	107.8
N1—C17—C18	111.86 (14)	B1—O2—C28	119.39 (18)

C14—C1—C2—C3	178.46 (18)	C8—C13—C14—C15	−176.70 (15)
C6—C1—C2—C3	−1.3 (3)	C1—C14—C15—N1	110.71 (18)
C1—C2—C3—C4	0.2 (3)	C13—C14—C15—N1	−72.1 (2)
C2—C3—C4—C5	0.6 (3)	C14—C15—N1—C16	−65.43 (19)
C3—C4—C5—C6	−0.1 (3)	C14—C15—N1—C17	172.57 (15)
C4—C5—C6—C7	180.00 (17)	C16—N1—C17—C18	167.01 (16)
C4—C5—C6—C1	−1.0 (3)	C15—N1—C17—C18	−69.96 (19)
C14—C1—C6—C7	1.0 (2)	N1—C17—C18—C19	112.94 (19)
C2—C1—C6—C7	−179.30 (16)	N1—C17—C18—C23	−63.2 (2)
C14—C1—C6—C5	−178.08 (16)	C23—C18—C19—C20	1.1 (3)
C2—C1—C6—C5	1.7 (2)	C17—C18—C19—C20	−175.04 (17)
C5—C6—C7—C8	178.75 (16)	C18—C19—C20—C21	−0.1 (3)
C1—C6—C7—C8	−0.2 (3)	C19—C20—C21—C22	−0.7 (3)
C5—C6—C7—Br1	−0.5 (2)	C20—C21—C22—C23	0.4 (3)
C1—C6—C7—Br1	−179.53 (12)	C21—C22—C23—C18	0.6 (3)
C6—C7—C8—C9	−179.51 (17)	C21—C22—C23—B1	179.1 (2)
Br1—C7—C8—C9	−0.2 (2)	C19—C18—C23—C22	−1.3 (3)
C6—C7—C8—C13	−0.3 (3)	C17—C18—C23—C22	174.77 (17)
Br1—C7—C8—C13	178.97 (12)	C19—C18—C23—B1	−179.76 (18)
C7—C8—C9—C10	179.77 (18)	C17—C18—C23—B1	−3.7 (3)
C13—C8—C9—C10	0.6 (3)	C22—C23—B1—O1	145.6 (2)
C8—C9—C10—C11	−0.1 (3)	C18—C23—B1—O1	−36.0 (3)
C9—C10—C11—C12	−0.6 (3)	C22—C23—B1—O2	−32.0 (3)
C10—C11—C12—C13	0.8 (3)	C18—C23—B1—O2	146.40 (19)
C11—C12—C13—C14	179.93 (18)	O2—B1—O1—C24	−0.8 (3)
C11—C12—C13—C8	−0.3 (3)	B1—O1—C24—C25	−27.9 (3)
C7—C8—C13—C14	0.2 (2)	O1—C24—C25—C28	52.9 (3)
C9—C8—C13—C14	179.42 (16)	C24—C25—C28—O2	−52.7 (3)
C7—C8—C13—C12	−179.62 (16)	C25—C28—O2—B1	27.3 (3)
C9—C8—C13—C12	−0.4 (2)	O1—B1—O2—C28	1.2 (3)
C2—C1—C14—C13	179.18 (16)	C23—B1—O1—C24	−178.20 (18)
C6—C1—C14—C13	−1.1 (2)	C23—B1—O2—C28	178.75 (18)
C2—C1—C14—C15	−3.7 (3)	O1—C24—C25—C26	−68.2 (2)
C6—C1—C14—C15	176.01 (15)	O1—C24—C25—C27	170.64 (19)
C12—C13—C14—C1	−179.68 (16)	C26—C25—C28—O2	67.5 (3)
C8—C13—C14—C1	0.5 (2)	C27—C25—C28—O2	−170.9 (2)
C12—C13—C14—C15	3.1 (2)

Acknowledgements

GEMM acknowledges funding for this work received from the National Research Foundation of the Republic of South Africa (Economic Growth and Development Fund, Gun 2053369).

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