3-[1-(4-Bromo­phen­yl)eth­oxy]-2,2,5-trimethyl-4-phenyl-3-aza­hexa­ne

Pitliya, P.; Butcher, R.J.; Karim, A.; Hudrlik, P.F.; Hudrlik, A.M.; Raghavan, D.

doi:10.1107/S1600536813029966

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages o1792-o1793

doi:10.1107/S1600536813029966

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3-[1-(4-Bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane

Praveen Pitliya,^a Ray J. Butcher,^a ^* A. Karim,^b Paul F. Hudrlik,^a Anne M. Hudrlik ^a and D. Raghavan ^a

^aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^bDepartment of Polymer Engineering, University of Akron, Akron, OH, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 27 September 2013; accepted 1 November 2013; online 20 November 2013)

The title compound, C₂₂H₃₀BrNO, is an alkoxyamine compound, an effective initiator in nitroxide-mediated free radical polymerization. It was prepared as a mixture of two diasteromers; the crystal for the X-ray analysis showed one of these as a pair of R,S and S,R enantiomers. The tert-butyl and isopropyl groups are in an almost anti conformation in the crystal [C—N—C—C torsion angle = −168.8 (1)°], and the methyl group of the ethoxy group is in an approximate anti relationship to the tert-butyl group. The dihedral angle between the phenyl and benzene rings is 33.12 (7)°. The Br atom is disordered over two positions, with occupancies of 0.9139 (16) and 0.0861 (16). In the crystal, weak C—H⋯Br contacts link the molecules into chains along [-110].

CCDC reference: 969901

Related literature

For the use of TIPNO-based alkoxyamine in polymer synthesis (TIPNO = 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide), see: Benoit et al. (1999 ). For the synthesis of the title compound, see: Kaul et al. (2010 ). For the use of the title compound in block copolymer synthesis, see: Richard et al. (2008 ); Kaul et al. (2010); Stalmach et al. (2001 ); van der Veen et al. (2004 ); Widin et al. (2013 ). For properties of alkoxyamines, see: Benoit et al. (1999); Wetter et al. (2004 ); Rodlert et al. (2000 ); Nilsen & Braslau (2006 ). For synthesis of 1-(4-bromophenyl) ethylbromide, see: Kodama et al. (2011 ); Thompson et al. (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₂H₃₀BrNO
M_r = 404.38
Triclinic, $[P \overline 1]$
a = 8.2595 (4) Å
b = 10.0175 (4) Å
c = 12.5257 (6) Å
α = 88.798 (4)°
β = 78.824 (4)°
γ = 89.220 (3)°
V = 1016.45 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 123 K
0.51 × 0.35 × 0.06 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.375, T_max = 0.888
23820 measured reflections
13014 independent reflections
7448 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.123
S = 1.08
13014 reflections
237 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯Br1Aⁱ	0.98	3.12	3.9782 (16)	148
C13—H13A⋯Br1Aⁱⁱ	1.00	3.07	4.0358 (13)	163
C13—H13A⋯Br1Bⁱⁱ	1.00	3.02	3.970 (2)	159
C15—H15B⋯Br1Bⁱⁱ	0.98	3.14	4.017 (3)	149
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 969901

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813029966/hg5350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029966/hg5350Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813029966/hg5350Isup3.cml

checkCIF report

Comment top

Nitroxide-mediated radical polymerization (NMRP) has been widely used under mild conditions to synthesize polymers and block copolymers with controlled molecular weight, polydispersity, and end group functionality (Benoit et al., 1999; Wetter et al., 2004). In NMRP, an alkoxyamine is used to initiate and mediate polymerization. The C–O bond of an alkoxyamine is stable to normal purification and handling procedures as well as variety of reaction conditions (Rodlert et al., 2000). However, under appropriate conditions, homolysis of the C—O bond occurs, giving a (relatively stable) nitroxide radical and carbon radical which can initiate radical polymerization. The nitroxides are kinetically persistent radicals, and act as reversible traps for the less stable radical intermediates in the polymerization (Nilsen & Braslau, 2006).

Alkoxyamines based on 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) have been widely used as initiators/mediators to synthesize a variety of linear polymers and block copolymers (van der Veen et al., 2004; Widin et al., 2013). In particular, alkoxyamine 2 (X = H; Figure 4), was found to be especially useful in NMRP (Benoit et al., 1999). The title compound, bromo analog 1 (X = Br) was developed so that 2 could be attached to a polymer, to give a macroinitiator for block copolymer synthesis (Stalmach et al., 2001). It has been used successfully in a number of block copolymer syntheses including polystyrene-b-poly(3-hexylthiophene) (PS-b-P3HT) (Kaul et al., 2010), poly(phenylenevinylene)-b-poly(butylacrylate) (PPV-b-PBA) (Stalmach et al., 2001), and poly(3-hexylthiophene)-b-poly(butylacrylate-stat-C60methylstyrene {P3HT-b-[P(BA-stat-C60MS)]} (Richard et al., 2008). Examples of block copolymers, prepared by TIPNO-mediated polymerizations, that have been successfully utilized in photovoltaic application are poly[(2,5-di(2'ethyl)hexyloxy)-1,4-phenylenevinylene]-b-poly(butylacrylate-stat-C60methylstyrene) [DEH-PPV-b-P(BA-stat-C60MS)], poly(vinyltriphenylamine)-b-poly(perylene bisimide acrylate) (PvTPA-b-PPerAcr) and poly(3-hexylthiophene)-b-poly(perylene bisimide acrylate (P3HT-b-PPerAcr).

The title compound was prepared as a mixture of two diastereomers in nearly equal amounts, as can be seen by the NMR spectrum (Figure 3). The crystal for the X-ray analysis showed one of the diastereomers (Figure 1), a pair of R,S and S,R (at C7 and C13) enantiomers. The tert-butyl group and isopropyl group are in a nearly anti conformation in the crystal (dihedral angle C9, N1, C13, C14 = -168.8 (1)°). The C—Me bond (C7, C8) and N-tert-Bu bond (N1, C9) are in an anti relationship (C8, C7, N1, C9 = 172.3 (1)°), and the C—Me bond (C7, C8) and C-isopropyl bond (C13, C14) are in a syn relationship (C8, C7, C13, C14 = 4.6 (1) degrees). The dihedral angle between the planes of the phenyl groups is 33.12 (7)°.

The bromine atom was disordered over two positions with occupancies of 0.9139 (16) and 0.0961 (16). The central N is pyramidal and all the bond lengths and angles are in the normal ranges (Allen et al., 1987). There are weak C—H···Br intermolecular contacts which link the molecules into chains in the [1 1 0] direction.

Related literature top

For the use of TIPNO-based alkoxyamine in polymer synthesis (TIPNO = 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide), see: Benoit et al. (1999). For the synthesis of the title compound, see: Kaul et al. (2010). For the use of the title compound in block copolymer synthesis, see: Richard et al. (2008); Kaul et al. (2010); Stalmach et al. (2001); van der Veen et al. (2004); Widin et al. (2013). For properties of alkoxyamines, see: Benoit et al. (1999); Wetter et al. (2004); Rodlert et al. (2000); Nilsen & Braslau (2006). For synthesis of 1-(4-bromophenyl) ethylbromide, see: Kodama et al. (2011); Thompson et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

(a) 1-(4-Bromophenyl)ethylbromide

1-(4-Bromophenyl)ethylbromide was synthesized according to previously reported procedures. 4-Bromoacetophenone was reduced to 1-(4-bromophenyl)ethanol by sodium borohydride (Kodama et al., 2011), and the product was treated with PBr₃ using a procedure of Thompson (Thompson et al., 2011). 1-(4-Bromophenyl)ethylbromide (Kaul et al., 2010) was obtained as colorless liquid in 70% overall yield.

(b) 3-[1-(4-Bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane (1)

3-[1-(4-Bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane was synthesized according to a previously reported method [Kaul et al., 2010] with a modification of the time and temperature. Synthesized 1-(4-bromophenyl) ethylbromide and commercially available 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) were reacted in the presence of CuBr and N,N,N'',N',N''-pentamethyldiethylenetriamine (PMDETA) in toluene at 75 ^oC for 17 hr to form the title compound (1), 3-[1-(4-bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane, in 80% yield as a viscous colorless oil which slowly crystallized in the refrigerator. The synthesized compound was characterized by ¹H NMR and its crystal structure was determined by X-ray crystallography. The ¹H NMR spectrum (Figure 3) showed the presence of two diastereomers in nearly equal amounts, and was in agreement with the published spectrum (Kaul et al., 2010). A crystal was taken for X-ray crystallography.

¹H NMR (400 MHz, CDCl₃) (mixture of two diastereomers): δ = 7.55–7.15 (HAr), 4.89 (H5 and H5'), 3.43 (H3), 3.31 (H3'), 2.31 (H2), 1.58 (H6), 1.53 (H6'), 1.42 (H2'), 1.26 (H1), 1.04 (H4'), 0.93 (H1'), 0.78 (H4), 0.54 (H1), 0.25 (H1').

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structural diagram of the title compound. Atomic displacement parameters are at the 30% probability level.
	Fig. 2. Packing diagram of the title compound viewed along the a axis.
	Fig. 3. ¹H NMR spectrum of 3-[1-(4-bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane (two diastereomers) in CDCl₃
	Fig. 4. Alkoxyamine 2 (X = H) and the title compound, bromo analog 1 (X = Br).

3-[1-(4-Bromophenyl)ethoxy]-2,2,5-trimethyl-4-phenyl-3-azahexane top

Crystal data top

C₂₂H₃₀BrNO	Z = 2
M_r = 404.38	F(000) = 424
Triclinic, P1	D_x = 1.321 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2595 (4) Å	Cell parameters from 4369 reflections
b = 10.0175 (4) Å	θ = 3.2–40.9°
c = 12.5257 (6) Å	µ = 2.03 mm⁻¹
α = 88.798 (4)°	T = 123 K
β = 78.824 (4)°	Diamond shaped plate, colorless
γ = 89.220 (3)°	0.51 × 0.35 × 0.06 mm
V = 1016.45 (8) Å³

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	13014 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 10.5081 pixels mm^-1	θ_max = 41.0°, θ_min = 3.2°
ω scans	h = −13→15
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	k = −18→18
T_min = 0.375, T_max = 0.888	l = −16→22
23820 measured reflections

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0319P)² + 0.3044P] where P = (F_o² + 2F_c²)/3
13014 reflections	(Δ/σ)_max = 0.002
237 parameters	Δρ_max = 0.71 e Å⁻³
14 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

C₂₂H₃₀BrNO	γ = 89.220 (3)°
M_r = 404.38	V = 1016.45 (8) Å³
Triclinic, P1	Z = 2
a = 8.2595 (4) Å	Mo Kα radiation
b = 10.0175 (4) Å	µ = 2.03 mm⁻¹
c = 12.5257 (6) Å	T = 123 K
α = 88.798 (4)°	0.51 × 0.35 × 0.06 mm
β = 78.824 (4)°

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	13014 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	7448 reflections with I > 2σ(I)
T_min = 0.375, T_max = 0.888	R_int = 0.040
23820 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	14 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.08	Δρ_max = 0.71 e Å⁻³
13014 reflections	Δρ_min = −0.78 e Å⁻³
237 parameters

Special details top

Experimental. CrysAlisPro (Agilent, 2012) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark & Reid, 1995)

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	Occ. (<1)
Br1A	−0.21657 (3)	1.03569 (3)	0.31920 (3)	0.03904 (8)	0.9139 (16)
Br1B	−0.2097 (3)	1.0344 (3)	0.2954 (4)	0.03904 (8)	0.0861 (16)
O1	0.33888 (11)	0.52249 (9)	0.26150 (7)	0.02013 (18)
N1	0.42054 (13)	0.41412 (11)	0.31003 (9)	0.0184 (2)
C1	0.22930 (16)	0.73932 (14)	0.30589 (11)	0.0213 (2)
C2	0.21935 (18)	0.85614 (15)	0.36510 (12)	0.0263 (3)
H2A	0.3043	0.8757	0.4036	0.032*
C3	0.08780 (19)	0.94442 (15)	0.36896 (13)	0.0282 (3)
H3A	0.0825	1.0244	0.4089	0.034*
C4	−0.03621 (15)	0.91347 (13)	0.31314 (12)	0.0255 (3)
C5	−0.03140 (18)	0.79814 (15)	0.25483 (12)	0.0260 (3)
H5A	−0.1177	0.7784	0.2175	0.031*
C6	0.10213 (17)	0.71062 (15)	0.25143 (11)	0.0235 (3)
H6A	0.1066	0.6306	0.2116	0.028*
C7	0.38199 (16)	0.65120 (14)	0.29630 (12)	0.0243 (3)
H7A	0.4127	0.6411	0.3695	0.029*
C8	0.5227 (2)	0.71609 (18)	0.21809 (15)	0.0361 (4)
H8A	0.6227	0.6610	0.2138	0.054*
H8B	0.5424	0.8050	0.2440	0.054*
H8C	0.4943	0.7243	0.1458	0.054*
C9	0.29326 (17)	0.35139 (15)	0.39863 (11)	0.0228 (3)
C10	0.25278 (19)	0.45110 (17)	0.49164 (12)	0.0297 (3)
H10A	0.1974	0.5298	0.4670	0.045*
H10B	0.3551	0.4782	0.5133	0.045*
H10C	0.1800	0.4089	0.5539	0.045*
C11	0.3726 (2)	0.22698 (17)	0.44159 (13)	0.0338 (4)
H11A	0.3849	0.1568	0.3872	0.051*
H11B	0.3021	0.1950	0.5092	0.051*
H11C	0.4813	0.2497	0.4559	0.051*
C12	0.13032 (17)	0.31498 (16)	0.36504 (13)	0.0276 (3)
H12A	0.1510	0.2450	0.3104	0.041*
H12B	0.0841	0.3942	0.3342	0.041*
H12C	0.0520	0.2825	0.4290	0.041*
C13	0.49844 (15)	0.32510 (13)	0.21998 (10)	0.0188 (2)
H13A	0.5453	0.2479	0.2563	0.023*
C14	0.64814 (15)	0.39403 (15)	0.14855 (10)	0.0209 (2)
H14A	0.6102	0.4801	0.1192	0.025*
C15	0.77943 (17)	0.42426 (17)	0.21525 (12)	0.0273 (3)
H15A	0.8661	0.4789	0.1713	0.041*
H15B	0.8277	0.3404	0.2367	0.041*
H15C	0.7287	0.4729	0.2805	0.041*
C16	0.72633 (18)	0.30662 (18)	0.05259 (12)	0.0303 (3)
H16A	0.8242	0.3510	0.0108	0.045*
H16B	0.6463	0.2931	0.0055	0.045*
H16C	0.7585	0.2200	0.0802	0.045*
C17	0.38509 (16)	0.26336 (14)	0.15192 (10)	0.0203 (2)
C18	0.3761 (2)	0.12507 (16)	0.14801 (12)	0.0283 (3)
H18A	0.4397	0.0712	0.1881	0.034*
C19	0.2754 (2)	0.06402 (18)	0.08627 (13)	0.0363 (4)
H19A	0.2704	−0.0306	0.0847	0.044*
C20	0.1827 (2)	0.1417 (2)	0.02737 (13)	0.0372 (4)
H20A	0.1125	0.1007	−0.0138	0.045*
C21	0.19305 (18)	0.27933 (18)	0.02873 (12)	0.0299 (3)
H21A	0.1304	0.3327	−0.0124	0.036*
C22	0.29426 (17)	0.34049 (15)	0.08968 (11)	0.0232 (3)
H22A	0.3016	0.4351	0.0890	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1A	0.03220 (8)	0.02458 (8)	0.0589 (2)	0.01144 (6)	−0.00651 (9)	0.00285 (9)
Br1B	0.03220 (8)	0.02458 (8)	0.0589 (2)	0.01144 (6)	−0.00651 (9)	0.00285 (9)
O1	0.0218 (4)	0.0146 (4)	0.0256 (4)	0.0023 (3)	−0.0084 (3)	−0.0031 (3)
N1	0.0176 (4)	0.0182 (5)	0.0187 (5)	0.0036 (4)	−0.0019 (4)	−0.0007 (4)
C1	0.0193 (5)	0.0165 (5)	0.0273 (6)	−0.0007 (4)	−0.0026 (5)	−0.0019 (5)
C2	0.0260 (6)	0.0197 (6)	0.0342 (7)	0.0003 (5)	−0.0079 (5)	−0.0059 (5)
C3	0.0305 (7)	0.0169 (6)	0.0357 (7)	0.0018 (5)	−0.0020 (6)	−0.0042 (5)
C4	0.0219 (6)	0.0173 (6)	0.0346 (7)	0.0035 (5)	0.0004 (5)	0.0046 (5)
C5	0.0217 (6)	0.0256 (7)	0.0310 (7)	0.0031 (5)	−0.0061 (5)	−0.0009 (5)
C6	0.0204 (5)	0.0207 (6)	0.0295 (6)	0.0011 (5)	−0.0043 (5)	−0.0060 (5)
C7	0.0187 (5)	0.0182 (6)	0.0367 (7)	−0.0001 (5)	−0.0067 (5)	−0.0058 (5)
C8	0.0243 (7)	0.0267 (8)	0.0543 (10)	−0.0028 (6)	0.0009 (7)	−0.0064 (7)
C9	0.0204 (5)	0.0230 (6)	0.0229 (6)	0.0009 (5)	0.0011 (5)	0.0002 (5)
C10	0.0278 (7)	0.0352 (8)	0.0232 (6)	−0.0001 (6)	0.0025 (5)	−0.0050 (6)
C11	0.0355 (8)	0.0317 (8)	0.0307 (7)	0.0048 (7)	0.0008 (6)	0.0089 (6)
C12	0.0206 (6)	0.0255 (7)	0.0342 (7)	−0.0038 (5)	0.0018 (5)	−0.0030 (6)
C13	0.0181 (5)	0.0182 (5)	0.0200 (5)	0.0024 (4)	−0.0036 (4)	−0.0023 (4)
C14	0.0165 (5)	0.0248 (6)	0.0208 (6)	0.0017 (5)	−0.0024 (4)	−0.0032 (5)
C15	0.0188 (5)	0.0360 (8)	0.0281 (7)	0.0005 (5)	−0.0060 (5)	−0.0057 (6)
C16	0.0221 (6)	0.0413 (9)	0.0260 (7)	0.0020 (6)	−0.0001 (5)	−0.0110 (6)
C17	0.0179 (5)	0.0213 (6)	0.0209 (6)	−0.0003 (5)	−0.0012 (4)	−0.0039 (4)
C18	0.0334 (7)	0.0221 (6)	0.0289 (7)	−0.0010 (6)	−0.0047 (6)	−0.0042 (5)
C19	0.0455 (9)	0.0276 (8)	0.0352 (8)	−0.0129 (7)	−0.0048 (7)	−0.0080 (6)
C20	0.0352 (8)	0.0463 (10)	0.0315 (8)	−0.0160 (7)	−0.0075 (6)	−0.0078 (7)
C21	0.0232 (6)	0.0421 (9)	0.0253 (7)	−0.0041 (6)	−0.0067 (5)	−0.0032 (6)
C22	0.0206 (5)	0.0266 (7)	0.0222 (6)	0.0001 (5)	−0.0031 (5)	−0.0035 (5)

Geometric parameters (Å, º) top

Br1A—C4	1.9064 (11)	C11—H11B	0.9800
Br1B—C4	1.9064 (15)	C11—H11C	0.9800
O1—C7	1.4406 (17)	C12—H12A	0.9800
O1—N1	1.4540 (14)	C12—H12B	0.9800
N1—C13	1.4922 (16)	C12—H12C	0.9800
N1—C9	1.5061 (18)	C13—C17	1.5274 (18)
C1—C2	1.3916 (19)	C13—C14	1.5409 (19)
C1—C6	1.3948 (19)	C13—H13A	1.0000
C1—C7	1.5165 (18)	C14—C15	1.5285 (19)
C2—C3	1.386 (2)	C14—C16	1.5350 (19)
C2—H2A	0.9500	C14—H14A	1.0000
C3—C4	1.389 (2)	C15—H15A	0.9800
C3—H3A	0.9500	C15—H15B	0.9800
C4—C5	1.376 (2)	C15—H15C	0.9800
C5—C6	1.3942 (19)	C16—H16A	0.9800
C5—H5A	0.9500	C16—H16B	0.9800
C6—H6A	0.9500	C16—H16C	0.9800
C7—C8	1.512 (2)	C17—C18	1.391 (2)
C7—H7A	1.0000	C17—C22	1.3975 (19)
C8—H8A	0.9800	C18—C19	1.396 (2)
C8—H8B	0.9800	C18—H18A	0.9500
C8—H8C	0.9800	C19—C20	1.383 (3)
C9—C10	1.535 (2)	C19—H19A	0.9500
C9—C11	1.536 (2)	C20—C21	1.384 (3)
C9—C12	1.536 (2)	C20—H20A	0.9500
C10—H10A	0.9800	C21—C22	1.392 (2)
C10—H10B	0.9800	C21—H21A	0.9500
C10—H10C	0.9800	C22—H22A	0.9500
C11—H11A	0.9800

C7—O1—N1	111.94 (9)	C9—C11—H11C	109.5
O1—N1—C13	107.20 (9)	H11A—C11—H11C	109.5
O1—N1—C9	107.14 (9)	H11B—C11—H11C	109.5
C13—N1—C9	116.38 (11)	C9—C12—H12A	109.5
C2—C1—C6	118.76 (12)	C9—C12—H12B	109.5
C2—C1—C7	119.47 (12)	H12A—C12—H12B	109.5
C6—C1—C7	121.66 (12)	C9—C12—H12C	109.5
C3—C2—C1	121.23 (14)	H12A—C12—H12C	109.5
C3—C2—H2A	119.4	H12B—C12—H12C	109.5
C1—C2—H2A	119.4	N1—C13—C17	117.31 (10)
C2—C3—C4	118.61 (13)	N1—C13—C14	110.32 (11)
C2—C3—H3A	120.7	C17—C13—C14	112.06 (10)
C4—C3—H3A	120.7	N1—C13—H13A	105.4
C5—C4—C3	121.74 (11)	C17—C13—H13A	105.4
C5—C4—Br1A	120.07 (11)	C14—C13—H13A	105.4
C3—C4—Br1A	118.19 (11)	C15—C14—C16	108.65 (11)
C5—C4—Br1B	114.39 (18)	C15—C14—C13	110.80 (11)
C3—C4—Br1B	123.43 (18)	C16—C14—C13	111.31 (12)
Br1A—C4—Br1B	8.81 (16)	C15—C14—H14A	108.7
C4—C5—C6	118.94 (13)	C16—C14—H14A	108.7
C4—C5—H5A	120.5	C13—C14—H14A	108.7
C6—C5—H5A	120.5	C14—C15—H15A	109.5
C5—C6—C1	120.72 (13)	C14—C15—H15B	109.5
C5—C6—H6A	119.6	H15A—C15—H15B	109.5
C1—C6—H6A	119.6	C14—C15—H15C	109.5
O1—C7—C8	113.22 (12)	H15A—C15—H15C	109.5
O1—C7—C1	106.94 (10)	H15B—C15—H15C	109.5
C8—C7—C1	109.28 (12)	C14—C16—H16A	109.5
O1—C7—H7A	109.1	C14—C16—H16B	109.5
C8—C7—H7A	109.1	H16A—C16—H16B	109.5
C1—C7—H7A	109.1	C14—C16—H16C	109.5
C7—C8—H8A	109.5	H16A—C16—H16C	109.5
C7—C8—H8B	109.5	H16B—C16—H16C	109.5
H8A—C8—H8B	109.5	C18—C17—C22	118.35 (13)
C7—C8—H8C	109.5	C18—C17—C13	119.09 (12)
H8A—C8—H8C	109.5	C22—C17—C13	122.51 (12)
H8B—C8—H8C	109.5	C17—C18—C19	121.19 (15)
N1—C9—C10	107.73 (12)	C17—C18—H18A	119.4
N1—C9—C11	107.59 (11)	C19—C18—H18A	119.4
C10—C9—C11	108.01 (12)	C20—C19—C18	119.81 (16)
N1—C9—C12	115.25 (11)	C20—C19—H19A	120.1
C10—C9—C12	107.66 (11)	C18—C19—H19A	120.1
C11—C9—C12	110.36 (13)	C19—C20—C21	119.62 (15)
C9—C10—H10A	109.5	C19—C20—H20A	120.2
C9—C10—H10B	109.5	C21—C20—H20A	120.2
H10A—C10—H10B	109.5	C20—C21—C22	120.69 (15)
C9—C10—H10C	109.5	C20—C21—H21A	119.7
H10A—C10—H10C	109.5	C22—C21—H21A	119.7
H10B—C10—H10C	109.5	C21—C22—C17	120.29 (15)
C9—C11—H11A	109.5	C21—C22—H22A	119.9
C9—C11—H11B	109.5	C17—C22—H22A	119.9
H11A—C11—H11B	109.5

C7—O1—N1—C13	−130.22 (11)	O1—N1—C9—C12	50.03 (14)
C7—O1—N1—C9	104.18 (12)	C13—N1—C9—C12	−69.86 (15)
C6—C1—C2—C3	−1.2 (2)	O1—N1—C13—C17	−58.63 (14)
C7—C1—C2—C3	175.04 (14)	C9—N1—C13—C17	61.23 (15)
C1—C2—C3—C4	0.7 (2)	O1—N1—C13—C14	71.30 (12)
C2—C3—C4—C5	0.1 (2)	C9—N1—C13—C14	−168.84 (10)
C2—C3—C4—Br1A	179.95 (11)	N1—C13—C14—C15	61.24 (14)
C2—C3—C4—Br1B	−171.8 (2)	C17—C13—C14—C15	−166.09 (11)
C3—C4—C5—C6	−0.3 (2)	N1—C13—C14—C16	−177.74 (11)
Br1A—C4—C5—C6	179.81 (11)	C17—C13—C14—C16	−45.06 (15)
Br1B—C4—C5—C6	172.24 (17)	N1—C13—C17—C18	−120.29 (14)
C4—C5—C6—C1	−0.2 (2)	C14—C13—C17—C18	110.60 (14)
C2—C1—C6—C5	0.9 (2)	N1—C13—C17—C22	62.25 (17)
C7—C1—C6—C5	−175.21 (14)	C14—C13—C17—C22	−66.86 (15)
N1—O1—C7—C8	95.05 (14)	C22—C17—C18—C19	−1.9 (2)
N1—O1—C7—C1	−144.54 (10)	C13—C17—C18—C19	−179.49 (14)
C2—C1—C7—O1	162.77 (13)	C17—C18—C19—C20	0.2 (2)
C6—C1—C7—O1	−21.13 (18)	C18—C19—C20—C21	1.1 (3)
C2—C1—C7—C8	−74.34 (17)	C19—C20—C21—C22	−0.7 (2)
C6—C1—C7—C8	101.77 (16)	C20—C21—C22—C17	−1.0 (2)
O1—N1—C9—C10	−70.17 (13)	C18—C17—C22—C21	2.3 (2)
C13—N1—C9—C10	169.94 (11)	C13—C17—C22—C21	179.79 (12)
O1—N1—C9—C11	173.61 (11)	C8—C7—C13—C14	4.56 (11)
C13—N1—C9—C11	53.72 (15)	C8—C7—N1—C9	172.28 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···Br1Aⁱ	0.98	3.12	3.9782 (16)	148
C13—H13A···Br1Aⁱⁱ	1.00	3.07	4.0358 (13)	163
C13—H13A···Br1Bⁱⁱ	1.00	3.02	3.970 (2)	159
C15—H15B···Br1Bⁱⁱ	0.98	3.14	4.017 (3)	149

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···Br1Aⁱ	0.98	3.12	3.9782 (16)	147.6
C13—H13A···Br1Aⁱⁱ	1.00	3.07	4.0358 (13)	162.7
C13—H13A···Br1Bⁱⁱ	1.00	3.02	3.970 (2)	158.6
C15—H15B···Br1Bⁱⁱ	0.98	3.14	4.017 (3)	149.3

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

Acknowledgements

DR and AK would like to thank the US Department of Energy, Division of Basic Energy Sciences under contract No. DE–FG02-10ER4779. RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer and the Howard University Nanoscience Facility for access to liquid nitrogen.

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