(−)-(P)-N,N′-Bis­[(5-bromo-2-hydroxy­phenyl)­methyl­idene]-6,6′-di­methyl-1,1′-bi­phenyl-2,2′-dimethan­amine

The absolute configuration of the enantiopure, axially chiral title compound, C₃₀H₂₆Br₂N₂O₂, has been determined. The mol­ecule has approximate C₂ symmetry and intramolecular O—H...N hydrogen bonds occur within each of the imine side chains of the mol­ecule. The planes of the bi­phenyl aromatic rings are bent significantly from the axis of the central C—C bond.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.048
• wR factor = 0.105
• Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.55
         From the CIF: _reflns_number_total               6049
         Count of symmetry unique reflns         3437
         Completeness (_total/calc)            176.00%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2612
         Fraction of Friedel pairs measured     0.760
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

S1. Comment

Axially chiral compounds containing a biphenyl moiety have been used extensively as chiral auxiliaries for asymmetric synthesis (Schmid et al., 1988), and we have been using some new axially chiral diimine ligands in asymmetric catalysis (Keller & Rippert, 1999). The title compound, (I), was synthesized by a condensation reaction between enantiomerically pure (P)-6,6'-dimethyl-1,1'-biphenyl-2,2'-dimethylamine and 5-bromosalicylealdehyde. The structure of (I) was determined in order to confirm the absolute configuration of the chiral axis. With this structure in hand, the correlation between the Cotton effect displayed by the CD-spectrum of (I) and those of related biphenyl compounds that we have synthesized could then be used to deduce the absolute configurations of these latter compounds (Keller & Rippert, 1999).

The refined value of the absolute structure parameter [0.013 (9); Flack & Bernardinelli, 2000] unambiguously confirmed that the title compound is enantiopure and that the chiral axis has the P-configuration. The angle between the planes of the two phenyl rings of the 1,1'-biphenyl moiety is 79.88 (14)°, where the acute angle is subtended by the two imine substituents. The ring planes, particularly that defined by C7–C12, are bent slightly away from the C1—C7 axis, so that neither atom C4 nor C10 lie on the continuation of this axis. Atoms C7 and C10 lie 0.104 (7) and 0.294 (12) Å, respectively, from the mean plane through the ring defined by atoms C1–C6, while atoms C1 and C4 lie 0.026 (8) and 0.036 (12) Å, respectively, from the mean plane through the ring defined by atoms C7–C12. An analysis of the conformations adopted by the biphenyl moieties in 682 error-free ordered organic structures stored in the Cambridge Structural Database (Version 5.24 of November, 2002; Allen, 2002) indicated that the bending of the ring planes away from the C1—C7 axis follows a normal distribution pattern with no or very little deviation being displayed by the largest proportion of the structures, but that deviations of the magnitude observed for (I) are also quite common.

The imine groups are almost coplanar with their adjacent 5-bromo-2-hydroxyphenyl groups. The r.m.s deviation of atoms N1, O1, Br1 and C16–C22 from their mean plane is 0.022 Å, with the maximum deviation being 0.041 (3) Å for atom N1. This planar system makes an angle of 76.84 (12)° with the plane of the adjacent phenyl ring defined by atoms C1–C6. In the other corresponding phenylimine moiety, the r.m.s. deviation of the constituent atoms from their mean plane is 0.020 Å, with the maximum deviation being 0.044 (3) Å for atom N2, and the plane makes an angle of 78.45 (11)° with the plane of the adjacent phenyl ring defined by atoms C7–C12. The planes of the phenylimine moieties lie such that the O···Br axes are almost parallel to the biphenyl C4···C10 axis. When viewed along the C4···C10 axis, the molecule has a distinct `W' conformation. The molecule has approximate C₂ symmetry about an axis passing perpendicularly through the mid-point of the C1—C7 bond. The r.m.s. deviation of the atoms of the molecule from perfect C₂ symmetry is 0.158 Å. Within each phenylimine moiety, the hydroxy group forms an intramolecular O—H···N hydrogen bond with the imine N atom (Table 1), thereby creating a six-membered loop which has a graph-set motif of S(6) (Bernstein et al., 1995).

S2. Experimental

The synthesis of the title compound has been described by Keller & Rippert (1999); m.p. 360 K. Spectroscopic analysis: [α]²⁵_D −20° (c 1.05, ethanol); CD spectrum (c 3.45 × 10⁻⁵, ethanol, λ, nm): 217 (−26.5), 235 (26.9), 254 (9.8), 263 (7.9), 318 (0.8), 349 (−0.25). Suitable crystals were obtained by cooling a saturated solution in ethanol to 273 K.

S3. Refinement

The hydroxy H atoms were located in a difference Fourier map and their positions were refined freely along with individual isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–0.99 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.

(-)-(P)—N,N'-bis[(5-bromo-2-hydroxyphenyl)methylidene]- 6,6'-dimethyl-1,1'-biphenyl-2,2'-dimethanamine

Crystal data

C30H26Br2N2O2	Dx = 1.534 Mg m^−3
Mr = 606.35	Melting point: 360 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 17.496 (5) Å	θ = 17.0–19.5°
b = 18.590 (2) Å	µ = 3.12 mm^−1
c = 8.074 (7) Å	T = 173 K
V = 2626 (2) Å^3	Prism, yellow
Z = 4	0.38 × 0.28 × 0.23 mm
F(000) = 1224

Data collection

Rigaku AFC-5R diffractometer	3460 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.047
Graphite monochromator	θmax = 27.6°, θmin = 2.6°
ω–2θ scans	h = −22→22
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = −24→24
Tmin = 0.384, Tmax = 0.632	l = −10→10
8236 measured reflections	3 standard reflections every 150 reflections
6049 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0382P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.002
6049 reflections	Δρmax = 0.41 e Å^−3
336 parameters	Δρmin = −0.59 e Å^−3
0 restraints	Absolute structure: Flack & Bernardinelli (2000); 2630 Friedel pairs
Primary atom site location: heavy-atom method	Absolute structure parameter: 0.013 (9)

Special details

Experimental. Solvent used: EtOH Crystal mount: glued on a glass fibre

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

15.8843 (0.0149) x + 7.6353 (0.0146) y + 0.6776 (0.0091) z = 12.9665 (0.0119)

* 0.0412 (0.0032) N1 * −0.0381 (0.0035) C16 * −0.0108 (0.0042) C17 * −0.0020 (0.0044) C18 * 0.0105 (0.0040) C19 * 0.0106 (0.0041) C20 * 0.0026 (0.0042) C21 * 0.0216 (0.0041) C22 * −0.0239 (0.0031) O1 * −0.0116 (0.0023) Br1

Rms deviation of fitted atoms = 0.0216

−8.1003 (0.0298) x + 11.1895 (0.0276) y − 5.2531 (0.0121) z = 0.7531 (0.0316)

Angle to previous plane (with approximate e.s.d.) = 76.84 (0.12)

* 0.0038 (0.0031) C1 * −0.0069 (0.0031) C2 * 0.0005 (0.0032) C3 * 0.0093 (0.0032) C4 * −0.0125 (0.0031) C5 * 0.0059 (0.0031) C6 0.1042 (0.0070) C7 0.2939 (0.0116) C10

Rms deviation of fitted atoms = 0.0075

13.0973 (0.0249) x + 11.5857 (0.0292) y − 1.8268 (0.0163) z = 15.5224 (0.0176)

Angle to previous plane (with approximate e.s.d.) = 79.88 (0.14)

* −0.0028 (0.0031) C7 * −0.0030 (0.0033) C8 * 0.0082 (0.0035) C9 * −0.0077 (0.0036) C10 * 0.0019 (0.0036) C11 * 0.0034 (0.0032) C12 − 0.0261 (0.0075) C1 − 0.0363 (0.0123) C4

Rms deviation of fitted atoms = 0.0052

13.3795 (0.0188) x − 7.8018 (0.0157) y + 3.9475 (0.0076) z = 1.8157 (0.0207)

Angle to previous plane (with approximate e.s.d.) = 78.45 (0.11)

* 0.0436 (0.0031) N2 * −0.0234 (0.0034) C24 * −0.0198 (0.0042) C25 * −0.0042 (0.0044) C26 * 0.0019 (0.0041) C27 * 0.0101 (0.0041) C28 * −0.0143 (0.0042) C29 * −0.0117 (0.0038) C30 * −0.0046 (0.0033) O2 * 0.0225 (0.0023) Br2

Rms deviation of fitted atoms = 0.0196

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.67162 (5)	0.27737 (3)	0.24918 (11)	0.0809 (3)
Br2	0.60606 (4)	1.09811 (3)	0.58183 (8)	0.05453 (19)
O1	0.5518 (2)	0.47872 (18)	0.7707 (5)	0.0472 (11)
H1	0.535 (3)	0.522 (3)	0.735 (8)	0.060 (18)*
O2	0.6695 (2)	0.9108 (2)	−0.0102 (5)	0.0456 (10)
H2	0.652 (3)	0.866 (3)	0.011 (6)	0.033 (15)*
N1	0.5215 (2)	0.57136 (19)	0.5340 (5)	0.0323 (10)
N2	0.5797 (2)	0.81491 (18)	0.1168 (5)	0.0276 (10)
C1	0.6119 (3)	0.7142 (2)	0.4338 (5)	0.0241 (10)
C2	0.5428 (3)	0.7020 (2)	0.5162 (6)	0.0264 (11)
C3	0.5218 (3)	0.7474 (2)	0.6439 (6)	0.0322 (12)
H3	0.4747	0.7394	0.6997	0.039*
C4	0.5677 (3)	0.8040 (3)	0.6920 (6)	0.0339 (13)
H4	0.5520	0.8352	0.7788	0.041*
C5	0.6370 (3)	0.8150 (2)	0.6127 (6)	0.0295 (12)
H5	0.6695	0.8528	0.6485	0.035*
C6	0.6599 (3)	0.7713 (2)	0.4810 (6)	0.0257 (11)
C7	0.6330 (2)	0.6691 (2)	0.2859 (6)	0.0260 (12)
C8	0.5986 (3)	0.6837 (2)	0.1323 (6)	0.0269 (11)
C9	0.6174 (3)	0.6418 (2)	−0.0046 (6)	0.0359 (13)
H9	0.5953	0.6518	−0.1097	0.043*
C10	0.6694 (3)	0.5846 (3)	0.0138 (7)	0.0408 (14)
H10	0.6814	0.5550	−0.0784	0.049*
C11	0.7023 (3)	0.5717 (2)	0.1626 (7)	0.0349 (13)
H11	0.7379	0.5334	0.1721	0.042*
C12	0.6856 (3)	0.6125 (2)	0.3008 (6)	0.0308 (12)
C13	0.7331 (3)	0.7877 (2)	0.3905 (6)	0.0343 (13)
H131	0.7614	0.8250	0.4503	0.051*
H132	0.7213	0.8046	0.2785	0.051*
H133	0.7643	0.7440	0.3838	0.051*
C14	0.7212 (3)	0.5954 (2)	0.4662 (6)	0.0378 (13)
H141	0.7603	0.5581	0.4519	0.057*
H142	0.6817	0.5780	0.5424	0.057*
H143	0.7449	0.6388	0.5119	0.057*
C15	0.4918 (3)	0.6394 (2)	0.4702 (7)	0.0350 (13)
H151	0.4400	0.6477	0.5155	0.042*
H152	0.4876	0.6366	0.3481	0.042*
C16	0.5435 (3)	0.5242 (2)	0.4311 (7)	0.0297 (12)
H16	0.5386	0.5341	0.3162	0.036*
C17	0.5763 (3)	0.4550 (2)	0.4825 (7)	0.0309 (13)
C18	0.5789 (3)	0.4360 (2)	0.6508 (7)	0.0345 (13)
C19	0.6098 (3)	0.3693 (2)	0.6950 (7)	0.0406 (14)
H19	0.6119	0.3560	0.8085	0.049*
C20	0.6371 (3)	0.3231 (2)	0.5771 (8)	0.0443 (14)
H20	0.6578	0.2779	0.6085	0.053*
C21	0.6342 (3)	0.3425 (2)	0.4130 (8)	0.0429 (15)
C22	0.6056 (3)	0.4089 (2)	0.3637 (6)	0.0375 (12)
H22	0.6062	0.4224	0.2502	0.045*
C23	0.5416 (3)	0.7448 (2)	0.1138 (6)	0.0277 (12)
H231	0.5137	0.7393	0.0079	0.033*
H232	0.5039	0.7424	0.2050	0.033*
C24	0.5653 (3)	0.8582 (2)	0.2340 (6)	0.0283 (11)
H24	0.5292	0.8446	0.3161	0.034*
C25	0.6028 (3)	0.9285 (2)	0.2469 (6)	0.0273 (10)
C26	0.6540 (3)	0.9513 (2)	0.1224 (6)	0.0315 (12)
C27	0.6890 (3)	1.0185 (2)	0.1379 (7)	0.0390 (14)
H27	0.7231	1.0347	0.0542	0.047*
C28	0.6746 (3)	1.0614 (2)	0.2738 (7)	0.0368 (13)
H28	0.6995	1.1066	0.2845	0.044*
C29	0.6241 (3)	1.0386 (2)	0.3939 (7)	0.0368 (13)
C30	0.5887 (3)	0.9725 (2)	0.3835 (6)	0.0302 (12)
H30	0.5551	0.9569	0.4687	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0971 (6)	0.0346 (3)	0.1110 (6)	0.0063 (3)	0.0688 (5)	−0.0001 (4)
Br2	0.0636 (4)	0.0392 (3)	0.0609 (4)	−0.0047 (3)	0.0095 (4)	−0.0220 (3)
O1	0.066 (3)	0.0302 (18)	0.046 (3)	0.0010 (19)	−0.009 (2)	−0.001 (2)
O2	0.058 (3)	0.038 (2)	0.041 (2)	−0.009 (2)	0.017 (2)	−0.0092 (19)
N1	0.038 (3)	0.0209 (18)	0.038 (3)	−0.0027 (18)	0.000 (2)	0.0026 (19)
N2	0.035 (2)	0.0235 (18)	0.024 (2)	0.0033 (17)	−0.007 (2)	0.0012 (18)
C1	0.030 (3)	0.0195 (19)	0.023 (2)	0.004 (2)	−0.006 (2)	0.004 (2)
C2	0.035 (3)	0.021 (2)	0.024 (3)	0.006 (2)	−0.005 (2)	0.003 (2)
C3	0.033 (3)	0.030 (2)	0.034 (3)	0.007 (2)	0.001 (3)	0.005 (2)
C4	0.044 (3)	0.033 (3)	0.024 (3)	0.010 (3)	−0.002 (3)	−0.002 (2)
C5	0.041 (3)	0.023 (2)	0.025 (3)	−0.001 (2)	−0.017 (3)	−0.003 (2)
C6	0.026 (3)	0.022 (2)	0.029 (3)	0.000 (2)	−0.006 (2)	0.001 (2)
C7	0.028 (3)	0.019 (2)	0.032 (3)	−0.002 (2)	−0.003 (2)	0.000 (2)
C8	0.030 (3)	0.024 (2)	0.027 (3)	−0.003 (2)	−0.005 (2)	−0.003 (2)
C9	0.047 (4)	0.031 (2)	0.030 (3)	0.002 (3)	−0.010 (3)	−0.006 (2)
C10	0.041 (3)	0.036 (3)	0.045 (3)	0.005 (3)	−0.006 (3)	−0.022 (3)
C11	0.026 (3)	0.031 (3)	0.048 (4)	0.000 (2)	−0.008 (3)	−0.013 (3)
C12	0.030 (3)	0.020 (2)	0.042 (3)	−0.001 (2)	−0.009 (3)	−0.001 (2)
C13	0.037 (3)	0.024 (2)	0.042 (3)	−0.005 (2)	−0.008 (3)	−0.001 (2)
C14	0.037 (3)	0.028 (2)	0.048 (4)	0.003 (3)	−0.014 (3)	0.003 (3)
C15	0.037 (3)	0.029 (2)	0.039 (3)	−0.003 (2)	−0.002 (3)	0.002 (2)
C16	0.030 (3)	0.026 (2)	0.034 (3)	−0.009 (2)	−0.006 (3)	0.001 (2)
C17	0.022 (3)	0.024 (2)	0.047 (4)	−0.008 (2)	0.001 (3)	−0.002 (2)
C18	0.032 (3)	0.024 (2)	0.048 (4)	−0.004 (2)	−0.002 (3)	0.000 (3)
C19	0.036 (3)	0.030 (2)	0.056 (4)	−0.007 (3)	−0.002 (3)	0.008 (2)
C20	0.031 (3)	0.027 (3)	0.075 (4)	−0.003 (2)	0.006 (3)	0.010 (3)
C21	0.034 (3)	0.023 (2)	0.071 (4)	−0.005 (2)	0.021 (3)	−0.005 (3)
C22	0.035 (3)	0.028 (2)	0.050 (3)	−0.007 (3)	0.011 (3)	0.001 (3)
C23	0.035 (3)	0.033 (2)	0.015 (3)	0.002 (2)	−0.011 (2)	−0.003 (2)
C24	0.033 (3)	0.025 (2)	0.027 (3)	0.005 (2)	−0.007 (2)	0.004 (2)
C25	0.032 (3)	0.0249 (19)	0.025 (3)	0.003 (2)	−0.001 (3)	0.002 (2)
C26	0.033 (3)	0.029 (2)	0.032 (3)	−0.001 (2)	0.001 (3)	0.002 (2)
C27	0.038 (3)	0.036 (3)	0.043 (4)	−0.005 (2)	0.008 (3)	0.001 (3)
C28	0.037 (3)	0.025 (2)	0.049 (4)	0.000 (2)	−0.004 (3)	−0.002 (3)
C29	0.037 (3)	0.032 (2)	0.042 (4)	0.003 (2)	−0.004 (3)	−0.011 (3)
C30	0.031 (3)	0.029 (2)	0.031 (3)	0.005 (2)	−0.001 (2)	0.003 (2)

Geometric parameters (Å, º)

Br1—C21	1.909 (5)	C13—H131	0.9800
Br2—C29	1.904 (5)	C13—H132	0.9800
O1—C18	1.339 (6)	C13—H133	0.9800
O1—H1	0.91 (5)	C14—H141	0.9800
O2—C26	1.336 (6)	C14—H142	0.9800
O2—H2	0.90 (5)	C14—H143	0.9800
N1—C16	1.267 (6)	C15—H151	0.9900
N1—C15	1.462 (5)	C15—H152	0.9900
N2—C24	1.267 (6)	C16—C17	1.469 (6)
N2—C23	1.464 (5)	C16—H16	0.9500
C1—C2	1.398 (6)	C17—C22	1.385 (6)
C1—C6	1.407 (6)	C17—C18	1.405 (7)
C1—C7	1.505 (6)	C18—C19	1.397 (6)
C2—C3	1.382 (6)	C19—C20	1.369 (7)
C2—C15	1.512 (6)	C19—H19	0.9500
C3—C4	1.380 (7)	C20—C21	1.374 (8)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.387 (7)	C21—C22	1.389 (6)
C4—H4	0.9500	C22—H22	0.9500
C5—C6	1.396 (6)	C23—H231	0.9900
C5—H5	0.9500	C23—H232	0.9900
C6—C13	1.505 (7)	C24—C25	1.467 (6)
C7—C12	1.403 (6)	C24—H24	0.9500
C7—C8	1.405 (6)	C25—C30	1.394 (6)
C8—C9	1.391 (6)	C25—C26	1.411 (7)
C8—C23	1.520 (6)	C26—C27	1.397 (6)
C9—C10	1.407 (7)	C27—C28	1.380 (7)
C9—H9	0.9500	C27—H27	0.9500
C10—C11	1.353 (7)	C28—C29	1.379 (7)
C10—H10	0.9500	C28—H28	0.9500
C11—C12	1.381 (6)	C29—C30	1.379 (6)
C11—H11	0.9500	C30—H30	0.9500
C12—C14	1.508 (7)
C18—O1—H1	114 (4)	N1—C15—H151	109.3
C26—O2—H2	107 (3)	C2—C15—H151	109.3
C16—N1—C15	118.4 (4)	N1—C15—H152	109.3
C24—N2—C23	119.1 (4)	C2—C15—H152	109.3
C2—C1—C6	120.7 (4)	H151—C15—H152	107.9
C2—C1—C7	119.9 (4)	N1—C16—C17	122.6 (5)
C6—C1—C7	119.3 (4)	N1—C16—H16	118.7
C3—C2—C1	119.1 (4)	C17—C16—H16	118.7
C3—C2—C15	119.7 (5)	C22—C17—C18	120.1 (4)
C1—C2—C15	121.2 (4)	C22—C17—C16	119.5 (5)
C4—C3—C2	121.3 (5)	C18—C17—C16	120.4 (5)
C4—C3—H3	119.3	O1—C18—C19	118.6 (5)
C2—C3—H3	119.3	O1—C18—C17	122.6 (4)
C3—C4—C5	119.5 (5)	C19—C18—C17	118.9 (5)
C3—C4—H4	120.3	C20—C19—C18	120.9 (5)
C5—C4—H4	120.3	C20—C19—H19	119.5
C4—C5—C6	121.1 (4)	C18—C19—H19	119.5
C4—C5—H5	119.4	C19—C20—C21	119.5 (5)
C6—C5—H5	119.4	C19—C20—H20	120.2
C5—C6—C1	118.3 (4)	C21—C20—H20	120.2
C5—C6—C13	119.8 (4)	C20—C21—C22	121.5 (5)
C1—C6—C13	121.9 (4)	C20—C21—Br1	119.3 (4)
C12—C7—C8	120.1 (4)	C22—C21—Br1	119.2 (5)
C12—C7—C1	120.7 (4)	C17—C22—C21	119.0 (5)
C8—C7—C1	119.2 (4)	C17—C22—H22	120.5
C9—C8—C7	119.5 (4)	C21—C22—H22	120.5
C9—C8—C23	119.7 (4)	N2—C23—C8	111.4 (4)
C7—C8—C23	120.8 (4)	N2—C23—H231	109.3
C8—C9—C10	119.4 (5)	C8—C23—H231	109.3
C8—C9—H9	120.3	N2—C23—H232	109.3
C10—C9—H9	120.3	C8—C23—H232	109.3
C11—C10—C9	120.2 (5)	H231—C23—H232	108.0
C11—C10—H10	119.9	N2—C24—C25	122.0 (5)
C9—C10—H10	119.9	N2—C24—H24	119.0
C10—C11—C12	122.0 (4)	C25—C24—H24	119.0
C10—C11—H11	119.0	C30—C25—C26	120.0 (4)
C12—C11—H11	119.0	C30—C25—C24	120.0 (4)
C11—C12—C7	118.8 (5)	C26—C25—C24	120.0 (4)
C11—C12—C14	120.8 (4)	O2—C26—C27	119.1 (5)
C7—C12—C14	120.4 (4)	O2—C26—C25	122.1 (4)
C6—C13—H131	109.5	C27—C26—C25	118.9 (5)
C6—C13—H132	109.5	C28—C27—C26	120.6 (5)
H131—C13—H132	109.5	C28—C27—H27	119.7
C6—C13—H133	109.5	C26—C27—H27	119.7
H131—C13—H133	109.5	C29—C28—C27	119.9 (4)
H132—C13—H133	109.5	C29—C28—H28	120.1
C12—C14—H141	109.5	C27—C28—H28	120.1
C12—C14—H142	109.5	C28—C29—C30	121.3 (5)
H141—C14—H142	109.5	C28—C29—Br2	119.2 (4)
C12—C14—H143	109.5	C30—C29—Br2	119.5 (4)
H141—C14—H143	109.5	C29—C30—C25	119.4 (5)
H142—C14—H143	109.5	C29—C30—H30	120.3
N1—C15—C2	111.7 (4)	C25—C30—H30	120.3
C6—C1—C2—C3	0.8 (6)	C15—N1—C16—C17	178.1 (4)
C7—C1—C2—C3	−175.2 (4)	N1—C16—C17—C22	−174.1 (5)
C6—C1—C2—C15	−178.1 (4)	N1—C16—C17—C18	5.1 (7)
C7—C1—C2—C15	5.9 (6)	C22—C17—C18—O1	179.6 (4)
C1—C2—C3—C4	−0.4 (7)	C16—C17—C18—O1	0.3 (8)
C15—C2—C3—C4	178.4 (4)	C22—C17—C18—C19	−1.4 (7)
C2—C3—C4—C5	−1.1 (7)	C16—C17—C18—C19	179.4 (4)
C3—C4—C5—C6	2.4 (7)	O1—C18—C19—C20	178.9 (5)
C4—C5—C6—C1	−2.0 (7)	C17—C18—C19—C20	−0.2 (7)
C4—C5—C6—C13	176.1 (4)	C18—C19—C20—C21	0.2 (8)
C2—C1—C6—C5	0.4 (6)	C19—C20—C21—C22	1.3 (8)
C7—C1—C6—C5	176.5 (4)	C19—C20—C21—Br1	−179.5 (4)
C2—C1—C6—C13	−177.6 (4)	C18—C17—C22—C21	2.8 (7)
C7—C1—C6—C13	−1.6 (6)	C16—C17—C22—C21	−177.9 (4)
C2—C1—C7—C12	−101.6 (5)	C20—C21—C22—C17	−2.8 (8)
C6—C1—C7—C12	82.4 (5)	Br1—C21—C22—C17	178.0 (4)
C2—C1—C7—C8	77.7 (5)	C24—N2—C23—C8	−115.8 (5)
C6—C1—C7—C8	−98.3 (5)	C9—C8—C23—N2	−106.0 (5)
C12—C7—C8—C9	−0.2 (7)	C7—C8—C23—N2	73.7 (5)
C1—C7—C8—C9	−179.5 (4)	C23—N2—C24—C25	178.5 (4)
C12—C7—C8—C23	−179.9 (4)	N2—C24—C25—C30	−176.0 (4)
C1—C7—C8—C23	0.8 (6)	N2—C24—C25—C26	3.0 (7)
C7—C8—C9—C10	1.3 (7)	C30—C25—C26—O2	179.7 (4)
C23—C8—C9—C10	−179.1 (4)	C24—C25—C26—O2	0.6 (7)
C8—C9—C10—C11	−1.7 (8)	C30—C25—C26—C27	−0.8 (7)
C9—C10—C11—C12	1.2 (8)	C24—C25—C26—C27	−179.9 (4)
C10—C11—C12—C7	−0.1 (7)	O2—C26—C27—C28	−179.6 (5)
C10—C11—C12—C14	178.0 (5)	C25—C26—C27—C28	0.8 (8)
C8—C7—C12—C11	−0.3 (7)	C26—C27—C28—C29	−1.3 (8)
C1—C7—C12—C11	178.9 (4)	C27—C28—C29—C30	1.7 (8)
C8—C7—C12—C14	−178.5 (4)	C27—C28—C29—Br2	179.1 (4)
C1—C7—C12—C14	0.8 (6)	C28—C29—C30—C25	−1.7 (7)
C16—N1—C15—C2	−114.4 (5)	Br2—C29—C30—C25	−179.1 (4)
C3—C2—C15—N1	−102.7 (5)	C26—C25—C30—C29	1.2 (7)
C1—C2—C15—N1	76.2 (6)	C24—C25—C30—C29	−179.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.91 (5)	1.88 (6)	2.627 (6)	138 (5)
O2—H2···N2	0.90 (5)	1.80 (5)	2.588 (5)	145 (4)