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Volume 69 
Part 12 
Pages o1792-o1793  
December 2013  

Received 27 September 2013
Accepted 1 November 2013
Online 20 November 2013

Key indicators
Single-crystal X-ray study
T = 123 K
Mean [sigma](C-C) = 0.002 Å
Disorder in main residue
R = 0.066
wR = 0.123
Data-to-parameter ratio = 54.9
Details
Open access

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

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

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].

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[Benoit, D., Chaplinski, V., Braslau, R. & Hawker, C. J. (1999). J. Am. Chem. Soc. 121, 3904-3920.]). For the synthesis of the title compound, see: Kaul et al. (2010[Kaul, E., Senkovskyy, V., Tkachov, R., Bocharova, V., Komber, H., Stamm, M. & Kiriy, A. (2010). Macromolecules, 43, 77-81.]). For the use of the title compound in block copolymer synthesis, see: Richard et al. (2008[Richard, F., Brochon, C., Leclerc, N., Eckhardt, D., Heiser, T. & Hadziioannou, G. (2008). Macromol. Rapid Commun. 29, 885-891.]); Kaul et al. (2010[Kaul, E., Senkovskyy, V., Tkachov, R., Bocharova, V., Komber, H., Stamm, M. & Kiriy, A. (2010). Macromolecules, 43, 77-81.]); Stalmach et al. (2001[Stalmach, U., de Boer, B., Post, A. D., van Hutten, P. F. & Hadziioannou, G. (2001). Angew. Chem. Int. Ed. 40, 428-430.]); van der Veen et al. (2004[Veen, M. H. van der, de Boer, B., Stalmach, U., van de Wetering, K. I. & Hadziioannou, G. (2004). Macromolecules, 37, 3673-3684.]); Widin et al. (2013[Widin, J. M., Kim, M., Schmitt, A. K., Han, E., Gopalan, P. & Mahanthappa, M. K. (2013). Macromolecules, 46, 4472-4480.]). For properties of alk­oxy­amines, see: Benoit et al. (1999[Benoit, D., Chaplinski, V., Braslau, R. & Hawker, C. J. (1999). J. Am. Chem. Soc. 121, 3904-3920.]); Wetter et al. (2004[Wetter, C., Gierlich, J., Knoop, C. A., Müller, C., Schulte, T. & Studer, A. (2004). Chem. Eur. J. 10, 1156-1166.]); Rodlert et al. (2000[Rodlert, M., Harth, E., Rees, I. & Hawker, C. J. (2000). J. Polym. Sci. Part A Polym. Chem. 38, 4749-4763.]); Nilsen & Braslau (2006[Nilsen, A. & Braslau, R. (2006). J. Polym. Sci. Part A Polym. Chem. 44, 697-717.]). For synthesis of 1-(4-bromo­phen­yl) ethyl­bromide, see: Kodama et al. (2011[Kodama, S., Hashidate, S., Nomoto, A., Yano, S., Ueshima, M. & Ogawa, A. (2011). Chem. Lett. 40, 495-497.]); Thompson et al. (2011[Thompson, A. M., Sutherland, H. S., Palmer, B. D., Kmentova, I., Blaser, A., Franzblau, S. G., Wan, B., Wang, Y., Ma, Z. & Denny, W. A. (2011). J. Med. Chem. 54, 6563-6585.]). For standard bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C22H30BrNO

  • Mr = 404.38

  • Triclinic, [P \overline 1]

  • a = 8.2595 (4) Å

  • b = 10.0175 (4) Å

  • c = 12.5257 (6) Å

  • [alpha] = 88.798 (4)°

  • [beta] = 78.824 (4)°

  • [gamma] = 89.220 (3)°

  • V = 1016.45 (8) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 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[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]), based on expressions derived by Clark & Reid (1995[Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.])] Tmin = 0.375, Tmax = 0.888

  • 23820 measured reflections

  • 13014 independent reflections

  • 7448 reflections with I > 2[sigma](I)

  • Rint = 0.040

Refinement
  • R[F2 > 2[sigma](F2)] = 0.066

  • wR(F2) = 0.123

  • S = 1.08

  • 13014 reflections

  • 237 parameters

  • 14 restraints

  • H-atom parameters constrained

  • [Delta][rho]max = 0.71 e Å-3

  • [Delta][rho]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[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG5350 ).


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.

References

Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.  [CrossRef]
Benoit, D., Chaplinski, V., Braslau, R. & Hawker, C. J. (1999). J. Am. Chem. Soc. 121, 3904-3920.  [Web of Science] [CrossRef] [ChemPort]
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.  [CrossRef] [IUCr Journals]
Kaul, E., Senkovskyy, V., Tkachov, R., Bocharova, V., Komber, H., Stamm, M. & Kiriy, A. (2010). Macromolecules, 43, 77-81.  [Web of Science] [CrossRef] [ChemPort]
Kodama, S., Hashidate, S., Nomoto, A., Yano, S., Ueshima, M. & Ogawa, A. (2011). Chem. Lett. 40, 495-497.  [Web of Science] [CrossRef] [ChemPort]
Nilsen, A. & Braslau, R. (2006). J. Polym. Sci. Part A Polym. Chem. 44, 697-717.  [CrossRef] [ChemPort]
Richard, F., Brochon, C., Leclerc, N., Eckhardt, D., Heiser, T. & Hadziioannou, G. (2008). Macromol. Rapid Commun. 29, 885-891.  [Web of Science] [CrossRef] [ChemPort]
Rodlert, M., Harth, E., Rees, I. & Hawker, C. J. (2000). J. Polym. Sci. Part A Polym. Chem. 38, 4749-4763.  [CrossRef] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Stalmach, U., de Boer, B., Post, A. D., van Hutten, P. F. & Hadziioannou, G. (2001). Angew. Chem. Int. Ed. 40, 428-430.  [Web of Science] [CrossRef] [ChemPort]
Thompson, A. M., Sutherland, H. S., Palmer, B. D., Kmentova, I., Blaser, A., Franzblau, S. G., Wan, B., Wang, Y., Ma, Z. & Denny, W. A. (2011). J. Med. Chem. 54, 6563-6585.  [Web of Science] [CrossRef] [ChemPort] [PubMed]
Veen, M. H. van der, de Boer, B., Stalmach, U., van de Wetering, K. I. & Hadziioannou, G. (2004). Macromolecules, 37, 3673-3684.
Wetter, C., Gierlich, J., Knoop, C. A., Müller, C., Schulte, T. & Studer, A. (2004). Chem. Eur. J. 10, 1156-1166.  [CrossRef] [PubMed] [ChemPort]
Widin, J. M., Kim, M., Schmitt, A. K., Han, E., Gopalan, P. & Mahanthappa, M. K. (2013). Macromolecules, 46, 4472-4480.  [Web of Science] [CrossRef] [ChemPort]


Acta Cryst (2013). E69, o1792-o1793   [ doi:10.1107/S1600536813029966 ]

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