research communications
of bis(3-bromomesityl)(quinolin-1-ium-8-yl)boron(III) tribromide
aDepartment of Chemistry, University of South Dakota, 414 E. Clark St, Vermillion, SD 57069, USA
*Correspondence e-mail: jhoefelm@usd.edu
The title compound, C27H26.82BBr2.18N+·Br3−, is a cationic triarylborane isolated as its tribromide salt. The aryl substituents include a protonated 8-quinolyl group and two 3-bromomesityl groups. The molecule was prepared on combination of 3:1 Br2 and dimesityl(quinolin-8-yl)borane in hexanes. The of the structure indicated a degree of `over-bromination' (beyond two bromine atoms) for the cation. There are two tribromide ions in the both completed by crystallographic inversion symmetry.
Keywords: crystal structure; frustrated Lewis pair; halogen; heterolysis; electrophilic aromatic substitution.
CCDC reference: 1419502
1. Chemical context
We recently prepared the preorganized unimolecular frustrated Lewis pair molecule 8-quinolyldimesitylborane (Son et al., 2010) and hypothesized that it could participate in the heterolytic cleavage of molecular bromine. Halogen addition to a frustrated Lewis pair was recently reported in the literature (Frömel et al., 2012). The combination of 8-quinolyldimesitylborane with three equivalents of Br2 in hexanes led to precipitation of the title compound. Features of the structure suggest heterolytic cleavage of Br2 occurred at the frustrated Lewis pair site. The bromination of the mesityl groups is likely due to electrophilic aromatic substitution from a brominium ion that yields HBr, manifest as a proton on the quinoline nitrogen atom and bromide bound to molecular bromine to form the tribromide ion. Alternatively, radical bromination of the solvent (hexane) yields HBr; however, a radical mechanism is not likely for the bromination of mesityl groups. Typically bromination of aromatics is performed with a catalyst and occurs through an electrophilic aromatic substitution mechanism.
2. Structural commentary
The title compound crystallizes in the P, and contains one cation and two half tribromide ions (completed by inversion symmetry) in the The cation (Fig. 1) features a planar three-coordinate triarylborane with two 3-bromomesityl groups and an 8-quinolyl group. The nitrogen atom is protonated and the positive charge is balanced by the presence of a tribromide anion, Br3−. The tribromide anions are shared between asymmetric units of the crystal, such that each unit contains two halves of an anion (Br5 and Br7 lie on crystallographic inversion centers). The Br5—Br6 distance is 2.5427 (11) Å and the Br7—Br8 distance is 2.546 (2) Å. Other bond distances and angles are given on Table 1. The mesityl groups are brominated at the meta positions such that one position is nearly completely brominated while the other meta position on the same ring is brominated to a much lesser extent. The best solution was found with refined bromine occupancy at the meta positions (C10 ring: Br1 = 0.95, Br4 = 0.09 for a total Br count of 1.04 on the ring; C19 ring: Br2 = 0.89, Br3 = 0.24 for a total Br count of 1.13 on the ring). The balance of electron density at the positions is accounted by partial hydrogen atoms at a reciprocal value of the bromine occupancy to give an overall formulation for the cation of C27H26.82BBr2.18N+.
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3. Supramolecular features
The cations are arranged in rows that propagate along the a-axis direction wherein each cation is in the same orientation due to translation along the row. Inversion centers are located on the dimesitylboryl side of the row, just beyond the brominated mesityl groups, and the packing of the cations in the crystal results in interdigitated parallel quinolinium rings; these symmetrically sandwich a tribromide anion, such that the central atom of the anion is located at an inversion center. A packing diagram is shown in Fig. 2.
4. Database survey
A search in the Cambridge Structural Database (Groom & Allen, 2014) for structures with the tribromide anion revealed 162 hits while a search for structures with the dimesitylboryl fragment revealed 539 hits. Among these are several structures of planar organic aromatic cations as tribromide salts. There are examples that display a cationic aromatic ring–tribromide–cationic aromatic ring motif (Manna et al., 2014), including 8-quinolinium derivatives (Müller et al., 2010; Rybakov et al., 2013) similar to the title compound. Alternatively, non-sandwich-type packing modes were found (Dean et al., 2009) including structures that feature π-stacking between aromatic cations (Bakshi et al. (1996), even 8-quinolinium derivatives (Thone et al. (2010).
5. Synthesis and crystallization
Reactions were performed using Schlenk and glovebox techniques under an atmosphere of N2 using dried and distilled solvents. Dimesityl(8-quinolyl)borane was prepared according to the literature (Son et al., 2010). A round-bottom air-free flask was charged with 110 mg (0.29 mmol) dimesityl(8-quinolyl)borane and 20 ml hexanes. In a separate flask, 2 ml of a solution of 5% Br2 in CCl4 (1 mmol Br2) was added to 10 ml hexanes and subjected to one freeze–pump–thaw cycle. The Br2 solution was transferred to the borane solution via a cannula at room temperature with stirring, and immediately a light-yellow precipitate formed. The solvent was removed in vacuo. Dichloromethane was added to the solid reside into which the title compound was dissolved; remaining insolubles were filtered off. Pale-yellow prisms of the title compound were grown by vapor diffusion of pentane into the methylene chloride solution.
6. Refinement
Crystal data, data collection, and structure . C-bound H atoms were refined using a riding model with C—H = 0.95 or 0.98 Å and with Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atom was freely refined.
details are summarized in Table 2Supporting information
CCDC reference: 1419502
https://doi.org/10.1107/S2056989015015467/hb7403sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015467/hb7403Isup2.hkl
Data collection: SMART (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C27H26.82BBr2.18N+·Br3− | Z = 2 |
Mr = 789.66 | F(000) = 764 |
Triclinic, P1 | Dx = 1.825 Mg m−3 |
a = 8.8469 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.2365 (13) Å | Cell parameters from 4521 reflections |
c = 14.7528 (18) Å | θ = 2.5–25.3° |
α = 79.600 (2)° | µ = 7.25 mm−1 |
β = 85.158 (2)° | T = 100 K |
γ = 87.994 (2)° | Prism, pale yellow |
V = 1437.0 (3) Å3 | 0.44 × 0.22 × 0.14 mm |
Bruker SMART CCD diffractometer | 5310 independent reflections |
Radiation source: sealed tube | 3409 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 25.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −10→10 |
Tmin = 0.161, Tmax = 0.362 | k = −13→13 |
14439 measured reflections | l = −17→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.156 | w = 1/[σ2(Fo2) + (0.0279P)2 + 15.1288P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
5310 reflections | Δρmax = 1.19 e Å−3 |
341 parameters | Δρmin = −1.37 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.5396 (12) | 0.6737 (8) | 0.5329 (8) | 0.047 (3) | |
H1 | 0.6369 | 0.6441 | 0.5502 | 0.057* | |
C2 | 0.5090 (13) | 0.6857 (10) | 0.4432 (8) | 0.055 (3) | |
H2 | 0.5840 | 0.6666 | 0.3978 | 0.066* | |
C3 | 0.3669 (13) | 0.7260 (10) | 0.4196 (8) | 0.054 (3) | |
H3 | 0.3434 | 0.7332 | 0.3572 | 0.065* | |
C4 | 0.1112 (12) | 0.8030 (8) | 0.4622 (7) | 0.047 (3) | |
H4 | 0.0848 | 0.8145 | 0.4001 | 0.056* | |
C5 | 0.0096 (12) | 0.8311 (8) | 0.5300 (7) | 0.045 (3) | |
H5 | −0.0890 | 0.8597 | 0.5147 | 0.054* | |
C6 | 0.0463 (11) | 0.8191 (8) | 0.6208 (7) | 0.036 (2) | |
H6 | −0.0270 | 0.8424 | 0.6656 | 0.043* | |
C7 | 0.1880 (10) | 0.7735 (8) | 0.6488 (7) | 0.036 (2) | |
C8 | 0.2927 (11) | 0.7434 (8) | 0.5796 (7) | 0.039 (2) | |
C9 | 0.2561 (12) | 0.7568 (8) | 0.4849 (7) | 0.040 (2) | |
C10 | 0.3368 (10) | 0.6643 (8) | 0.8014 (6) | 0.032 (2) | |
C11 | 0.4517 (11) | 0.7001 (8) | 0.8499 (6) | 0.035 (2) | |
C12 | 0.5639 (11) | 0.6170 (10) | 0.8818 (7) | 0.046 (3) | |
H12_b | 0.6450 | 0.6451 | 0.9101 | 0.055* | 0.911 (5) |
C13 | 0.5647 (11) | 0.4975 (9) | 0.8725 (7) | 0.040 (2) | |
C14 | 0.4479 (12) | 0.4607 (8) | 0.8295 (6) | 0.039 (2) | |
H14_c | 0.4436 | 0.3778 | 0.8244 | 0.046* | 0.047 (5) |
C15 | 0.3328 (11) | 0.5414 (9) | 0.7922 (7) | 0.042 (2) | |
C16 | 0.4624 (12) | 0.8290 (9) | 0.8694 (7) | 0.043 (3) | |
H16A | 0.3987 | 0.8841 | 0.8287 | 0.065* | |
H16B | 0.5680 | 0.8549 | 0.8579 | 0.065* | |
H16C | 0.4273 | 0.8304 | 0.9340 | 0.065* | |
C17 | 0.6889 (12) | 0.4110 (10) | 0.9100 (8) | 0.058 (3) | |
H17A | 0.6436 | 0.3361 | 0.9444 | 0.087* | |
H17B | 0.7458 | 0.4484 | 0.9513 | 0.087* | |
H17C | 0.7577 | 0.3923 | 0.8586 | 0.087* | |
C18 | 0.2075 (14) | 0.4930 (9) | 0.7468 (8) | 0.061 (3) | |
H18A | 0.1540 | 0.4300 | 0.7914 | 0.092* | |
H18B | 0.2510 | 0.4587 | 0.6937 | 0.092* | |
H18C | 0.1361 | 0.5589 | 0.7260 | 0.092* | |
C19 | 0.1088 (11) | 0.8376 (8) | 0.8148 (7) | 0.037 (2) | |
C20 | 0.0109 (12) | 0.7798 (9) | 0.8880 (7) | 0.044 (3) | |
C21 | −0.0971 (12) | 0.8503 (11) | 0.9318 (7) | 0.051 (3) | |
H21_a | −0.1628 | 0.8109 | 0.9816 | 0.061* | 0.761 (5) |
C22 | −0.1111 (12) | 0.9745 (11) | 0.9049 (7) | 0.049 (3) | |
C23 | −0.0117 (12) | 1.0276 (9) | 0.8338 (7) | 0.044 (3) | |
H23_d | −0.0193 | 1.1128 | 0.8142 | 0.052* | 0.106 (5) |
C24 | 0.1006 (11) | 0.9639 (9) | 0.7882 (7) | 0.039 (2) | |
C25 | 0.0069 (13) | 0.6444 (10) | 0.9180 (8) | 0.059 (3) | |
H25A | −0.0305 | 0.6078 | 0.8689 | 0.088* | |
H25B | −0.0609 | 0.6244 | 0.9744 | 0.088* | |
H25C | 0.1093 | 0.6130 | 0.9301 | 0.088* | |
C26 | −0.2310 (14) | 1.0438 (13) | 0.9548 (9) | 0.075 (4) | |
H26A | −0.3066 | 1.0785 | 0.9121 | 0.113* | |
H26B | −0.1833 | 1.1090 | 0.9775 | 0.113* | |
H26C | −0.2807 | 0.9888 | 1.0071 | 0.113* | |
C27 | 0.2097 (12) | 1.0305 (9) | 0.7132 (7) | 0.047 (3) | |
H27A | 0.1528 | 1.0739 | 0.6627 | 0.070* | |
H27B | 0.2808 | 0.9724 | 0.6896 | 0.070* | |
H27C | 0.2661 | 1.0886 | 0.7388 | 0.070* | |
B1 | 0.2151 (13) | 0.7594 (9) | 0.7547 (7) | 0.033 (3) | |
N1 | 0.4375 (10) | 0.7022 (7) | 0.5977 (6) | 0.039 (2) | |
Br1_c | 0.43924 (16) | 0.29439 (10) | 0.82058 (9) | 0.0618 (6) | 0.953 (5) |
Br2_d | −0.03034 (16) | 1.19837 (10) | 0.79562 (9) | 0.0541 (5) | 0.894 (5) |
Br3_a | −0.2186 (6) | 0.8077 (6) | 1.0259 (3) | 0.070 (3) | 0.239 (5) |
Br4_b | 0.6985 (17) | 0.619 (2) | 0.9386 (13) | 0.112 (11) | 0.089 (5) |
H1N | 0.474 (18) | 0.700 (14) | 0.655 (11) | 0.134* | |
Br5 | 0.5000 | 0.0000 | 0.5000 | 0.0421 (4) | |
Br6 | 0.35660 (13) | 0.06362 (10) | 0.35619 (8) | 0.0532 (4) | |
Br7 | 0.0000 | 0.5000 | 0.5000 | 0.0837 (8) | |
Br8 | 0.15880 (17) | 0.49848 (12) | 0.34799 (12) | 0.0921 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.051 (7) | 0.035 (6) | 0.058 (7) | 0.015 (5) | −0.007 (6) | −0.016 (5) |
C2 | 0.059 (8) | 0.059 (7) | 0.046 (7) | 0.020 (6) | −0.002 (6) | −0.013 (6) |
C3 | 0.060 (8) | 0.059 (7) | 0.047 (7) | 0.017 (6) | −0.006 (6) | −0.026 (6) |
C4 | 0.063 (8) | 0.035 (6) | 0.047 (7) | 0.013 (5) | −0.020 (6) | −0.014 (5) |
C5 | 0.043 (6) | 0.033 (5) | 0.060 (7) | 0.005 (5) | −0.018 (6) | −0.006 (5) |
C6 | 0.035 (6) | 0.028 (5) | 0.042 (6) | 0.010 (4) | −0.007 (5) | −0.002 (4) |
C7 | 0.029 (5) | 0.026 (5) | 0.052 (6) | 0.006 (4) | −0.007 (5) | −0.003 (4) |
C8 | 0.043 (6) | 0.026 (5) | 0.049 (6) | 0.009 (4) | −0.015 (5) | −0.008 (4) |
C9 | 0.053 (7) | 0.029 (5) | 0.042 (6) | 0.005 (5) | −0.017 (5) | −0.014 (4) |
C10 | 0.036 (6) | 0.028 (5) | 0.030 (5) | 0.006 (4) | 0.001 (4) | −0.005 (4) |
C11 | 0.038 (6) | 0.044 (6) | 0.023 (5) | 0.004 (5) | 0.003 (4) | −0.004 (4) |
C12 | 0.028 (6) | 0.057 (7) | 0.053 (7) | 0.001 (5) | −0.008 (5) | −0.011 (5) |
C13 | 0.033 (6) | 0.048 (6) | 0.038 (6) | 0.006 (5) | 0.002 (5) | −0.006 (5) |
C14 | 0.056 (7) | 0.022 (5) | 0.036 (6) | 0.005 (4) | 0.000 (5) | −0.004 (4) |
C15 | 0.045 (6) | 0.047 (6) | 0.035 (6) | 0.003 (5) | −0.014 (5) | −0.003 (5) |
C16 | 0.047 (6) | 0.052 (6) | 0.034 (6) | −0.004 (5) | −0.005 (5) | −0.015 (5) |
C17 | 0.045 (7) | 0.059 (7) | 0.072 (8) | 0.017 (6) | −0.016 (6) | −0.014 (6) |
C18 | 0.082 (9) | 0.027 (5) | 0.079 (9) | 0.001 (6) | −0.039 (7) | −0.005 (5) |
C19 | 0.040 (6) | 0.034 (5) | 0.039 (6) | 0.008 (4) | −0.016 (5) | −0.009 (4) |
C20 | 0.046 (6) | 0.053 (7) | 0.034 (6) | 0.014 (5) | −0.011 (5) | −0.006 (5) |
C21 | 0.040 (6) | 0.072 (8) | 0.037 (6) | 0.009 (6) | −0.002 (5) | 0.000 (6) |
C22 | 0.036 (6) | 0.074 (8) | 0.041 (6) | −0.001 (6) | −0.006 (5) | −0.017 (6) |
C23 | 0.053 (7) | 0.034 (5) | 0.048 (6) | 0.014 (5) | −0.023 (6) | −0.015 (5) |
C24 | 0.038 (6) | 0.043 (6) | 0.040 (6) | 0.009 (5) | −0.016 (5) | −0.012 (5) |
C25 | 0.049 (7) | 0.065 (8) | 0.056 (7) | 0.002 (6) | −0.003 (6) | 0.007 (6) |
C26 | 0.064 (9) | 0.107 (11) | 0.059 (8) | 0.021 (8) | 0.001 (7) | −0.037 (8) |
C27 | 0.048 (7) | 0.034 (6) | 0.057 (7) | 0.010 (5) | −0.010 (5) | −0.005 (5) |
B1 | 0.040 (7) | 0.028 (6) | 0.029 (6) | 0.003 (5) | −0.001 (5) | −0.001 (5) |
N1 | 0.044 (5) | 0.030 (4) | 0.044 (5) | 0.015 (4) | −0.008 (4) | −0.010 (4) |
Br1_c | 0.0883 (11) | 0.0296 (7) | 0.0724 (10) | 0.0149 (6) | −0.0404 (8) | −0.0099 (6) |
Br2_d | 0.0710 (10) | 0.0353 (7) | 0.0590 (9) | 0.0164 (6) | −0.0068 (7) | −0.0189 (6) |
Br3_a | 0.043 (3) | 0.138 (6) | 0.033 (3) | −0.012 (3) | −0.008 (2) | −0.021 (3) |
Br4_b | 0.037 (10) | 0.22 (3) | 0.085 (14) | 0.036 (11) | −0.026 (8) | −0.052 (14) |
Br5 | 0.0373 (8) | 0.0411 (8) | 0.0431 (9) | 0.0049 (6) | 0.0028 (7) | 0.0012 (6) |
Br6 | 0.0453 (7) | 0.0616 (7) | 0.0474 (7) | 0.0047 (5) | −0.0052 (5) | 0.0040 (5) |
Br7 | 0.0685 (12) | 0.0449 (10) | 0.1295 (18) | −0.0202 (9) | −0.0623 (12) | 0.0350 (10) |
Br8 | 0.0755 (10) | 0.0663 (9) | 0.1269 (13) | −0.0174 (7) | −0.0613 (9) | 0.0309 (8) |
C1—N1 | 1.333 (13) | C16—H16C | 0.9800 |
C1—C2 | 1.355 (14) | C17—H17A | 0.9800 |
C1—H1 | 0.9500 | C17—H17B | 0.9800 |
C2—C3 | 1.373 (14) | C17—H17C | 0.9800 |
C2—H2 | 0.9500 | C18—H18A | 0.9800 |
C3—C9 | 1.395 (14) | C18—H18B | 0.9800 |
C3—H3 | 0.9500 | C18—H18C | 0.9800 |
C4—C5 | 1.359 (14) | C19—C20 | 1.403 (14) |
C4—C9 | 1.410 (13) | C19—C24 | 1.403 (13) |
C4—H4 | 0.9500 | B1—C19 | 1.588 (14) |
C5—C6 | 1.388 (13) | C20—C21 | 1.409 (14) |
C5—H5 | 0.9500 | C20—C25 | 1.506 (14) |
C6—C7 | 1.404 (12) | C21—C22 | 1.385 (15) |
C6—H6 | 0.9500 | Br3_a—C21 | 1.690 (12) |
C7—C8 | 1.400 (13) | C21—H21_a | 0.9500 |
B1—C7 | 1.579 (14) | C22—C23 | 1.373 (15) |
C8—N1 | 1.378 (12) | C22—C26 | 1.513 (15) |
C8—C9 | 1.440 (13) | C23—C24 | 1.402 (13) |
C10—C11 | 1.402 (13) | C23—Br2_d | 1.905 (10) |
C10—C15 | 1.414 (13) | C23—H23_d | 0.9500 |
B1—C10 | 1.598 (13) | C24—C27 | 1.512 (14) |
C11—C12 | 1.390 (13) | C25—H25A | 0.9800 |
C11—C16 | 1.534 (13) | C25—H25B | 0.9800 |
C12—C13 | 1.374 (14) | C25—H25C | 0.9800 |
C12—Br4_b | 1.516 (17) | C26—H26A | 0.9800 |
C12—H12_b | 0.9500 | C26—H26B | 0.9800 |
C13—C14 | 1.370 (14) | C26—H26C | 0.9800 |
C13—C17 | 1.514 (13) | C27—H27A | 0.9800 |
C13—Br4_b | 2.24 (2) | C27—H27B | 0.9800 |
C14—C15 | 1.418 (13) | C27—H27C | 0.9800 |
Br1_c—C14 | 1.901 (9) | N1—H1N | 0.92 (15) |
C14—H14_c | 0.9500 | Br5—Br6i | 2.5427 (11) |
C15—C18 | 1.507 (14) | Br5—Br6 | 2.5427 (11) |
C16—H16A | 0.9800 | Br7—Br8 | 2.546 (2) |
C16—H16B | 0.9800 | Br7—Br8ii | 2.546 (2) |
N1—C1—C2 | 122.1 (10) | H17A—C17—H17C | 109.5 |
N1—C1—H1 | 119.0 | H17B—C17—H17C | 109.5 |
C2—C1—H1 | 119.0 | C15—C18—H18A | 109.5 |
C1—C2—C3 | 118.4 (10) | C15—C18—H18B | 109.5 |
C1—C2—H2 | 120.8 | H18A—C18—H18B | 109.5 |
C3—C2—H2 | 120.8 | C15—C18—H18C | 109.5 |
C2—C3—C9 | 121.7 (10) | H18A—C18—H18C | 109.5 |
C2—C3—H3 | 119.2 | H18B—C18—H18C | 109.5 |
C9—C3—H3 | 119.2 | C20—C19—C24 | 119.8 (9) |
C5—C4—C9 | 119.5 (9) | C20—C19—B1 | 119.9 (8) |
C5—C4—H4 | 120.3 | C24—C19—B1 | 119.8 (9) |
C9—C4—H4 | 120.3 | C19—C20—C21 | 118.8 (9) |
C4—C5—C6 | 121.7 (9) | C19—C20—C25 | 123.3 (9) |
C4—C5—H5 | 119.2 | C21—C20—C25 | 117.7 (10) |
C6—C5—H5 | 119.2 | C22—C21—C20 | 122.5 (10) |
C5—C6—C7 | 122.2 (9) | C22—C21—Br3_a | 108.2 (9) |
C5—C6—H6 | 118.9 | C20—C21—Br3_a | 129.2 (9) |
C7—C6—H6 | 118.9 | C22—C21—H21_a | 118.9 |
C8—C7—C6 | 116.4 (9) | C20—C21—H21_a | 118.6 |
C8—C7—B1 | 125.8 (8) | Br3_a—C21—H21_a | 11.3 |
C6—C7—B1 | 117.8 (9) | C23—C22—C21 | 116.7 (10) |
N1—C8—C7 | 121.9 (9) | C23—C22—C26 | 123.9 (11) |
N1—C8—C9 | 116.4 (9) | C21—C22—C26 | 119.4 (11) |
C7—C8—C9 | 121.7 (9) | C22—C23—C24 | 124.0 (9) |
C3—C9—C4 | 123.1 (9) | C22—C23—Br2_d | 117.2 (8) |
C3—C9—C8 | 118.4 (9) | C24—C23—Br2_d | 118.8 (8) |
C4—C9—C8 | 118.5 (9) | C22—C23—H23_d | 118.2 |
C11—C10—C15 | 118.3 (8) | C24—C23—H23_d | 117.8 |
C11—C10—B1 | 121.5 (8) | Br2_d—C23—H23_d | 1.0 |
C15—C10—B1 | 120.1 (8) | C23—C24—C19 | 118.0 (10) |
C12—C11—C10 | 119.7 (9) | C23—C24—C27 | 120.4 (9) |
C12—C11—C16 | 117.2 (9) | C19—C24—C27 | 121.6 (9) |
C10—C11—C16 | 123.1 (8) | C20—C25—H25A | 109.5 |
C13—C12—C11 | 123.3 (10) | C20—C25—H25B | 109.5 |
C13—C12—Br4_b | 101.3 (12) | H25A—C25—H25B | 109.5 |
C11—C12—Br4_b | 135.2 (13) | C20—C25—H25C | 109.5 |
C13—C12—H12_b | 118.7 | H25A—C25—H25C | 109.5 |
C11—C12—H12_b | 118.1 | H25B—C25—H25C | 109.5 |
Br4_b—C12—H12_b | 18.4 | C22—C26—H26A | 109.5 |
C14—C13—C12 | 117.2 (9) | C22—C26—H26B | 109.5 |
C14—C13—C17 | 122.1 (9) | H26A—C26—H26B | 109.5 |
C12—C13—C17 | 120.8 (9) | C22—C26—H26C | 109.5 |
C14—C13—Br4_b | 158.5 (9) | H26A—C26—H26C | 109.5 |
C12—C13—Br4_b | 41.7 (7) | H26B—C26—H26C | 109.5 |
C17—C13—Br4_b | 79.2 (8) | C24—C27—H27A | 109.5 |
C13—C14—C15 | 122.6 (9) | C24—C27—H27B | 109.5 |
C13—C14—Br1_c | 118.5 (7) | H27A—C27—H27B | 109.5 |
C15—C14—Br1_c | 118.8 (8) | C24—C27—H27C | 109.5 |
C13—C14—H14_c | 118.8 | H27A—C27—H27C | 109.5 |
C15—C14—H14_c | 118.5 | H27B—C27—H27C | 109.5 |
Br1_c—C14—H14_c | 0.6 | C7—B1—C10 | 121.6 (8) |
C10—C15—C14 | 118.8 (9) | C7—B1—C19 | 117.2 (8) |
C10—C15—C18 | 122.0 (8) | C10—B1—C19 | 121.0 (8) |
C14—C15—C18 | 119.2 (9) | C1—N1—C8 | 123.0 (9) |
C11—C16—H16A | 109.5 | C1—N1—H1N | 115 (10) |
C11—C16—H16B | 109.5 | C8—N1—H1N | 122 (10) |
H16A—C16—H16B | 109.5 | C14—Br1_c—H14_c | 0.6 |
C11—C16—H16C | 109.5 | C23—Br2_d—H23_d | 1.0 |
H16A—C16—H16C | 109.5 | C21—Br3_a—H21_a | 13.8 |
H16B—C16—H16C | 109.5 | C12—Br4_b—C13 | 37.1 (7) |
C13—C17—H17A | 109.5 | C12—Br4_b—H12_b | 26.0 |
C13—C17—H17B | 109.5 | C13—Br4_b—H12_b | 62.2 |
H17A—C17—H17B | 109.5 | Br6i—Br5—Br6 | 180.0 |
C13—C17—H17C | 109.5 | Br8—Br7—Br8ii | 180.0 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1. |
Acknowledgements
This work was supported by the National Science Foundation (CHE-0552687 and EPS-0554609) and the US Department of Energy (Contract Nos. DE–FG02-08ER64624 and DE–EE0000270).
References
Bakshi, P. K., James, M. A., Cameron, T. S. & Knop, O. (1996). Can. J. Chem. 74, 559–573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dean, P. M., Clare, B. R., Armel, V., Pringle, J. M., Forsyth, C. M., Forsyth, M. & MacFarlane, D. R. (2009). Aust. J. Chem. 62, 334. CSD CrossRef Google Scholar
Frömel, S., Fröhlich, R., Daniliuc, C. G., Kehr, G. & Erker, G. (2012). Eur. J. Inorg. Chem. pp. 3774–3779. Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Manna, P., Seth, S. K., Bauzá, A., Mitra, M., Ray Choudhury, S., Frontera, A. & Mukhopadhyay, S. (2014). Cryst. Growth Des. 14, 747–755. CSD CrossRef CAS Google Scholar
Müller, M., Albrecht, M., Gossen, V., Peters, T., Hoffmann, A., Raabe, G., Valkonen, A. & Rissanen, K. (2010). Chem. Eur. J. 16, 12446–12453. Web of Science PubMed Google Scholar
Rybakov, V. B., Shishkina, S. V., Ukrainets, I. V., Golik, N. Y. & Chernenok, I. N. (2013). Acta Cryst. E69, o82. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Son, J.-H., Pudenz, M. A. & Hoefelmeyer, J. D. (2010). Dalton Trans. 39, 11081–11090. CSD CrossRef CAS PubMed Google Scholar
Thone, C., Vancea, F., Bello, M. & Jones, P. G. (2010). Private Communication (Refcode QUWBUG). CCDC, Cambridge, England. Google Scholar
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