Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 7| July 2014| Pages o822-o823
https://doi.org/10.1107/S1600536814014433

2-Bromo-5-tert-butyl-N-methyl-N-[2-(methyl­amino)­phen­yl]-3-(1-methyl-1H-benzimidazol-2-yl)benzamide

Poonam Rajesh Prasad,a Shikha Das,a Harkesh B. Singha and Ray J. Butcherb*

aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India, and bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com

(Received 18 June 2014; accepted 19 June 2014; online 25 June 2014)

In the title compound, C27H29BrN4O, benzimidazole ring system and the amide moiety are planar [r.m.s. deviations = 0.016 (2) and 0.017 (1) Å, respectively]. The mol­ecule adopts a conformation in which the amide linkage is almost perpendicular to the central ring [dihedral angle = 85.79 (8)°], while the benzimidazole ring system makes a dihedral angle of 70.26 (11)° with the central ring. In the crystal, the mol­ecules form dimers through N—H⋯O hydrogen bonds and C—H⋯O interactions. These dimers are further linked into zigzag ribbons along [201] by weak C—H⋯Br inter­actions. As a result of the bulky nature of the mol­ecule, as evidenced by the large dihedral angles between rings, there is little evidence for any π–π inter­actions.

Keywords: crystal structure.

CCDC reference: 1009070

Similar articles

Related literature

The metal binding properties of imidazole-containing pincer ligands can be modified by the type of donor atoms and the electron-withdrawing and electron-releasing character of their substituents, see: Selander & Szabó (2011[Selander, N. J. & Szabó, K. (2011). Chem. Rev. 111, 2048-2076.]). For the effect of N-substitution on the catalytic activity of phosphinoimidazolines in palladium-catalysed Heck reactions, see: Busacca et al. (2003[Busacca, C. A., Grossbach, D., So, R. C., O'Brien, E. M. & Spinelli, E. M. (2003). Org. Lett. 5, 595-598.]). For the use of bromine-substituted benzimidazole in Heck reactions, see: Reddy & Krishna (2005[Reddy, K. R. & Krishna, G. G. (2005). Tetrahedron Lett. 46, 661-663.]). 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.]). For the preparation of the precursor, 2-bromo-5-(tert-but­yl)isophthalic acid, see: Field et al. (2003[Field, J. E., Hill, T. J. & Venkataraman, D. J. (2003). J. Org. Chem. 68, 6071-6078.]).

[Scheme 1]

Experimental

Crystal data

  • C27H29BrN4O

  • Mr = 505.45

  • Monoclinic, C 2/c

  • a = 34.4327 (13) Å

  • b = 9.4152 (2) Å

  • c = 17.1092 (7) Å

  • β = 118.312 (5)°

  • V = 4883.2 (3) Å3

  • Z = 8

  • Cu Kα radiation

  • μ = 2.50 mm−1

  • T = 123 K

  • 0.38 × 0.32 × 0.23 mm
Data collection

  • Agilent Xcalibur Ruby Gemini diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysalisAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]) Tmin = 0.788, Tmax = 1.000

  • 9307 measured reflections

  • 4929 independent reflections

  • 4100 reflections with I > 2σ(I)

  • Rint = 0.028
Refinement

  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.093

  • S = 1.03

  • 4929 reflections

  • 308 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.35 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H3B⋯O1i 0.81 (3) 2.35 (3) 3.038 (3) 143 (3)
C4—H4A⋯Brii 0.95 2.98 3.719 (3) 135
C12—H12A⋯O1i 0.95 2.37 3.287 (3) 163
Symmetry codes: (i) [-x+1, y, -z+{\script{1\over 2}}]; (ii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysalisAlis 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.

Supporting information

CCDC reference: 1009070

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014433/jj2190sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014433/jj2190Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814014433/jj2190Isup3.cml

checkCIF report


Experimental top

The methyl­ation reaction of 2 (Fig. 1) was carried out by reacting 1 (0.5 g, 1.12 mmol) with an excess of methyl iodide (1.75 g, 10 eq), followed by the addition of KOH (0.125 g, 2.24 mmol) in dry acetone (20 mL) and some molecular sieves. The reaction mixture was refluxed for 2 h. Then, it was diluted with ethyl acetate and washed with water. The organic layer was dried over Na2SO4 and purified by column chromatography to afford 2 which was crystallized from a mixture of di­chloro­methane and ether. Anal. Calcd. for C27H29BrON4: C, 64.16; H, 5.78; N, 11.08; found C, 64.30; H, 6.22; N, 9.17.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C—H distances of 0.95 and 0.98 Å Uiso(H) = 1.2Ueq(C) and 0.96 Å for CH3 [Uiso(H) = 1.5Ueq(C)]. The hydrogen atom attached to N3 was located in a difference Fourier and refined isotropically.

Comment top

The presence of imidazole rings in any molecular framework provides excellent modification sites for the fine tuning of properties related to electronic and steric factors. It has been reported in the literature that the strong electronic effect can be modified by the type of donor atoms and the electron-withdrawing and electron-releasing character of their substituents (Selander, & Szabó, 2011). Recently the effect of N-substitution on the catalytic activities of phosphinoimidazolines in palladium catalyzed Heck reactions has been reported (Busacca et al., 2003). Later, Reddy and co-workers (Reddy, & Krishna, 2005) have studied the use of bromine substituted benzimidazole in Heck reactions. Pincer ligands have immense scope in exploring different types of metal coordination chemistry and stabilizing unusual species. They provide the sites which can be easily fine tuned to synthesize a number of metal complexes/species, which can be stabilized by three coordinating/bonding units of the pincer ligands. There are no examples of selenium containing benzimidazoles known in the literature. Therefore, 2, 2'-(2-bromo-5-(tert-butyl)-1,3-diyl)bis­(1H-benzimidazole) (1) and its derivatives, having two coordinating imidazole rings were designed to incorporate selenium at 2-position of the phenyl group. An attempted methyl­ation of 1 led to cleavage of the one of the benzimidazole rings and resulted in the formation of unexpected compound 2 (Fig. 1). 2-Bromo-5-(tert-butyl)­isophthalic acid, the precursor for synthesizing 1, was prepared according to literature procedure (Field, et al., 2003). Compound 1 was synthesized by the reaction of 2-bromo-5-tert-butyl-isophthalic acid with 1,2-phenyl­enedi­amine in polyphospho­ric acid at 240°C.

In view of the above, the structure of the title compound, C27H29BrN4O, was determined (Fig. 2). The bond lengths and angles are all in the expected ranges (Allen et al., 1987) for such compounds. All the aromatic groups and the amide moiety are planar (rms deviations of 0.006 (1), 0.008 (2), 0.016 (2), and 0.017 (1) for the central phenyl ring, the substituent phenyl ring, the benzimidazole ring, and the amide moiety, respectively). The molecule adopts a conformation where the amide linkage is almost perpendicular to the central ring with a dihedral angle of 85.79 (8)° between central ring (C9–C14) and amide moiety (C19/C20/C21/N4/O1) while the benzimidazole ring makes a dihedral angle of 70.26° with the central ring. The molecules form dimers through N3—H···O1 inter­molecular hydrogen bonds (Fig. 3). These dimers are further linked into zig-zag ribbons in the [2 0 1] direction by weak C—H···Br inter­actions. Because of the bulky nature of the molecule, as evidenced by the large dihedral angles between rings, there is little evidence for any π–π inter­actions.

Related literature top

The strong electronic effect can be modified by the type of donor atoms and the electron-withdrawing and electron-releasing character of their substituents, see: Selander & Szabó (2011). For the effect of N-substitution on the catalytic activity of phosphinoimidazolines in palladium-catalysed Heck reactions, see: Busacca et al. (2003). For the use of bromine-substituted benzimidazole in Heck reactions, see: Reddy & Krishna (2005). For standard bond lengths, see: Allen et al. (1987). For the preparation of the precursor, 2-bromo-5-(tert-butyl)isophthalic acid, see: Field et al. (2003).

Structure description top

The methyl­ation reaction of 2 (Fig. 1) was carried out by reacting 1 (0.5 g, 1.12 mmol) with an excess of methyl iodide (1.75 g, 10 eq), followed by the addition of KOH (0.125 g, 2.24 mmol) in dry acetone (20 mL) and some molecular sieves. The reaction mixture was refluxed for 2 h. Then, it was diluted with ethyl acetate and washed with water. The organic layer was dried over Na2SO4 and purified by column chromatography to afford 2 which was crystallized from a mixture of di­chloro­methane and ether. Anal. Calcd. for C27H29BrON4: C, 64.16; H, 5.78; N, 11.08; found C, 64.30; H, 6.22; N, 9.17.

The presence of imidazole rings in any molecular framework provides excellent modification sites for the fine tuning of properties related to electronic and steric factors. It has been reported in the literature that the strong electronic effect can be modified by the type of donor atoms and the electron-withdrawing and electron-releasing character of their substituents (Selander, & Szabó, 2011). Recently the effect of N-substitution on the catalytic activities of phosphinoimidazolines in palladium catalyzed Heck reactions has been reported (Busacca et al., 2003). Later, Reddy and co-workers (Reddy, & Krishna, 2005) have studied the use of bromine substituted benzimidazole in Heck reactions. Pincer ligands have immense scope in exploring different types of metal coordination chemistry and stabilizing unusual species. They provide the sites which can be easily fine tuned to synthesize a number of metal complexes/species, which can be stabilized by three coordinating/bonding units of the pincer ligands. There are no examples of selenium containing benzimidazoles known in the literature. Therefore, 2, 2'-(2-bromo-5-(tert-butyl)-1,3-diyl)bis­(1H-benzimidazole) (1) and its derivatives, having two coordinating imidazole rings were designed to incorporate selenium at 2-position of the phenyl group. An attempted methyl­ation of 1 led to cleavage of the one of the benzimidazole rings and resulted in the formation of unexpected compound 2 (Fig. 1). 2-Bromo-5-(tert-butyl)­isophthalic acid, the precursor for synthesizing 1, was prepared according to literature procedure (Field, et al., 2003). Compound 1 was synthesized by the reaction of 2-bromo-5-tert-butyl-isophthalic acid with 1,2-phenyl­enedi­amine in polyphospho­ric acid at 240°C.

In view of the above, the structure of the title compound, C27H29BrN4O, was determined (Fig. 2). The bond lengths and angles are all in the expected ranges (Allen et al., 1987) for such compounds. All the aromatic groups and the amide moiety are planar (rms deviations of 0.006 (1), 0.008 (2), 0.016 (2), and 0.017 (1) for the central phenyl ring, the substituent phenyl ring, the benzimidazole ring, and the amide moiety, respectively). The molecule adopts a conformation where the amide linkage is almost perpendicular to the central ring with a dihedral angle of 85.79 (8)° between central ring (C9–C14) and amide moiety (C19/C20/C21/N4/O1) while the benzimidazole ring makes a dihedral angle of 70.26° with the central ring. The molecules form dimers through N3—H···O1 inter­molecular hydrogen bonds (Fig. 3). These dimers are further linked into zig-zag ribbons in the [2 0 1] direction by weak C—H···Br inter­actions. Because of the bulky nature of the molecule, as evidenced by the large dihedral angles between rings, there is little evidence for any π–π inter­actions.

The strong electronic effect can be modified by the type of donor atoms and the electron-withdrawing and electron-releasing character of their substituents, see: Selander & Szabó (2011). For the effect of N-substitution on the catalytic activity of phosphinoimidazolines in palladium-catalysed Heck reactions, see: Busacca et al. (2003). For the use of bromine-substituted benzimidazole in Heck reactions, see: Reddy & Krishna (2005). For standard bond lengths, see: Allen et al. (1987). For the preparation of the precursor, 2-bromo-5-(tert-butyl)isophthalic acid, see: Field et al. (2003).

Refinement details top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C—H distances of 0.95 and 0.98 Å Uiso(H) = 1.2Ueq(C) and 0.96 Å for CH3 [Uiso(H) = 1.5Ueq(C)]. The hydrogen atom attached to N3 was located in a difference Fourier and refined isotropically.

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
[Figure 1] Fig. 1. The structures of 1 and 2.
[Figure 2] Fig. 2. The molecular structure of C27H29BrN4O, showing the atom numbering scheme and 30% probability displacement ellipsoids and the linking of the molecules into dimers by N—H···O hydrogen bonds (shown as dashed bonds).
[Figure 3] Fig. 3. The molecular packing for C27H29BrN4O viewed along the b axis showing linking of the hydrogen bonded dimers into zigzag chains in the [2 0 1] direction by C—H···Br interactions (N—H···O and C—H···Br interactions shown as dashed bonds).
2-Bromo-5-tert-butyl-N-methyl-N-[2-(methylamino)phenyl]-3-(1-methyl-1H-benzimidazol-2-yl)benzamide top
Crystal data top
C27H29BrN4OF(000) = 2096
Mr = 505.45Dx = 1.375 Mg m−3
Monoclinic, C2/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2ycCell parameters from 4036 reflections
a = 34.4327 (13) Åθ = 2.9–75.5°
b = 9.4152 (2) ŵ = 2.50 mm−1
c = 17.1092 (7) ÅT = 123 K
β = 118.312 (5)°Prism, colorless
V = 4883.2 (3) Å30.38 × 0.32 × 0.23 mm
Z = 8
Data collection top
Agilent Xcalibur Ruby Gemini
diffractometer		4929 independent reflections
Radiation source: Enhance (Cu) X-ray Source4100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 10.5081 pixels mm-1θmax = 75.6°, θmin = 2.9°
ω scansh = −42→42
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		k = −8→11
Tmin = 0.788, Tmax = 1.000l = −20→21
9307 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0514P)2 + 0.4711P]
where P = (Fo2 + 2Fc2)/3
4929 reflections(Δ/σ)max = 0.004
308 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.35 e Å−3
Crystal data top
C27H29BrN4OV = 4883.2 (3) Å3
Mr = 505.45Z = 8
Monoclinic, C2/cCu Kα radiation
a = 34.4327 (13) ŵ = 2.50 mm−1
b = 9.4152 (2) ÅT = 123 K
c = 17.1092 (7) Å0.38 × 0.32 × 0.23 mm
β = 118.312 (5)°
Data collection top
Agilent Xcalibur Ruby Gemini
diffractometer		4929 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		4100 reflections with I > 2σ(I)
Tmin = 0.788, Tmax = 1.000Rint = 0.028
9307 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.43 e Å−3
4929 reflectionsΔρmin = −0.35 e Å−3
308 parameters
Special details top

Experimental. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.87-7.71 (1H, m), 7.46-7.31 (4H, m), 7.09-7.07 (1H, m), 6.54-6.48 (1H, m), 3.53 (2H, s), 3.45 (2H, s), 2.89 (2H, s), 1.38 (1H, s), 1.13 (6H, s). 13C NMR (CDCl3): δ 29.4, 30.9, 31.1, 31.9, 31.2, 34.7, 35.1, 35.5, 53.9, 109.7, 109.9, 120.2, 122.1, 122.5, 122.7, 123.1, 123.3, 129.4, 129.7, 131.2, 133.0, 135.6, 142.8, 151.7, 152.6, 152.8.

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
xyzUiso*/Ueq
Br0.630352 (8)0.53882 (3)0.543344 (15)0.03435 (9)
O10.52147 (5)0.66100 (17)0.36987 (11)0.0338 (3)
N10.70366 (6)0.3018 (2)0.53797 (13)0.0370 (4)
N20.65609 (7)0.1320 (2)0.53017 (14)0.0380 (4)
N30.56938 (7)0.7887 (2)0.19074 (15)0.0406 (5)
H3B0.5490 (9)0.765 (3)0.1989 (18)0.033 (7)*
N40.57538 (6)0.78517 (19)0.36118 (13)0.0315 (4)
C10.72063 (8)0.4328 (3)0.52039 (19)0.0447 (6)
H1A0.69980.46840.46140.067*
H1B0.74920.41420.52270.067*
H1C0.72440.50390.56530.067*
C20.72791 (8)0.2049 (3)0.60366 (16)0.0401 (5)
C30.77297 (9)0.1991 (4)0.66449 (19)0.0541 (7)
H3A0.79290.27170.66820.065*
C40.78664 (11)0.0803 (4)0.7190 (2)0.0620 (9)
H4A0.81710.06970.76000.074*
C50.75708 (12)−0.0240 (4)0.7155 (2)0.0615 (8)
H5A0.7679−0.10200.75540.074*
C60.71279 (11)−0.0174 (3)0.6561 (2)0.0542 (7)
H6A0.6929−0.08920.65410.065*
C70.69805 (8)0.1004 (3)0.59819 (16)0.0402 (5)
C80.66112 (7)0.2518 (2)0.49703 (15)0.0323 (4)
C90.62557 (7)0.3270 (2)0.42009 (14)0.0292 (4)
C100.60873 (7)0.2663 (2)0.33589 (15)0.0300 (4)
H10A0.61980.17690.32970.036*
C110.57614 (7)0.3331 (2)0.26044 (14)0.0292 (4)
C120.55997 (7)0.4627 (2)0.27251 (15)0.0294 (4)
H12A0.53710.50860.22240.035*
C130.57612 (6)0.5266 (2)0.35517 (14)0.0264 (4)
C140.60895 (7)0.4577 (2)0.42851 (14)0.0276 (4)
C150.55815 (8)0.2676 (2)0.16780 (16)0.0358 (5)
C160.59482 (11)0.1859 (3)0.15917 (19)0.0543 (7)
H16A0.60420.10430.19960.081*
H16B0.62000.24900.17440.081*
H16C0.58350.15240.09800.081*
C170.52108 (12)0.1646 (4)0.1534 (2)0.0693 (11)
H17A0.49780.21570.15920.104*
H17B0.53280.08880.19790.104*
H17C0.50890.12320.09380.104*
C180.54015 (8)0.3820 (3)0.09601 (15)0.0363 (5)
H18A0.51310.42230.09250.054*
H18B0.53360.34000.03870.054*
H18C0.56220.45730.11080.054*
C190.55554 (7)0.6638 (2)0.36324 (13)0.0275 (4)
C200.55836 (9)0.9201 (2)0.3754 (2)0.0426 (6)
H20A0.53620.90110.39470.064*
H20B0.54480.97430.31990.064*
H20C0.58270.97510.42120.064*
C210.61458 (7)0.7918 (2)0.35017 (17)0.0326 (5)
C220.65527 (8)0.8083 (3)0.42439 (18)0.0414 (5)
H22A0.65740.80920.48180.050*
C230.69305 (8)0.8234 (3)0.4155 (2)0.0511 (7)
H23A0.72110.83360.46640.061*
C240.68929 (8)0.8235 (3)0.3315 (2)0.0507 (7)
H24A0.71510.83330.32510.061*
C250.64900 (8)0.8098 (3)0.2569 (2)0.0435 (6)
H25A0.64740.81010.20000.052*
C260.60991 (7)0.7951 (2)0.26395 (17)0.0346 (5)
C270.56379 (9)0.7866 (3)0.10141 (18)0.0464 (6)
H27A0.53230.77940.05880.070*
H27B0.57950.70470.09450.070*
H27C0.57580.87430.09050.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.03690 (13)0.03680 (13)0.02700 (13)0.00268 (9)0.01323 (10)−0.00251 (9)
O10.0297 (7)0.0358 (8)0.0387 (8)−0.0016 (6)0.0186 (7)−0.0021 (7)
N10.0310 (9)0.0397 (10)0.0355 (10)0.0022 (8)0.0118 (8)0.0008 (9)
N20.0409 (10)0.0310 (9)0.0377 (10)0.0037 (8)0.0151 (9)0.0023 (8)
N30.0332 (10)0.0481 (12)0.0406 (11)−0.0087 (9)0.0175 (9)−0.0048 (9)
N40.0269 (9)0.0257 (8)0.0416 (10)0.0007 (7)0.0159 (8)−0.0004 (8)
C10.0359 (12)0.0481 (14)0.0495 (15)−0.0062 (11)0.0196 (12)−0.0017 (12)
C20.0389 (12)0.0445 (13)0.0324 (12)0.0115 (10)0.0132 (10)0.0003 (10)
C30.0398 (14)0.072 (2)0.0381 (14)0.0112 (13)0.0085 (12)−0.0019 (14)
C40.0498 (16)0.083 (2)0.0357 (14)0.0283 (16)0.0059 (13)0.0053 (15)
C50.071 (2)0.0625 (19)0.0414 (15)0.0313 (17)0.0189 (15)0.0140 (14)
C60.0675 (19)0.0453 (15)0.0460 (15)0.0195 (14)0.0237 (15)0.0108 (12)
C70.0439 (13)0.0377 (12)0.0349 (12)0.0119 (10)0.0153 (11)0.0026 (10)
C80.0334 (11)0.0304 (10)0.0312 (11)0.0043 (9)0.0138 (9)−0.0007 (9)
C90.0270 (10)0.0282 (10)0.0307 (11)−0.0011 (8)0.0124 (9)0.0003 (8)
C100.0302 (10)0.0243 (9)0.0355 (11)−0.0010 (8)0.0155 (9)−0.0012 (8)
C110.0321 (10)0.0241 (9)0.0313 (11)−0.0072 (8)0.0150 (9)−0.0027 (8)
C120.0292 (10)0.0267 (10)0.0294 (10)−0.0019 (8)0.0115 (9)0.0023 (8)
C130.0246 (9)0.0239 (9)0.0302 (10)−0.0031 (8)0.0125 (8)−0.0007 (8)
C140.0279 (10)0.0289 (10)0.0249 (10)−0.0031 (8)0.0117 (8)−0.0022 (8)
C150.0483 (13)0.0268 (10)0.0300 (11)−0.0073 (10)0.0167 (10)−0.0028 (9)
C160.082 (2)0.0392 (13)0.0388 (14)0.0177 (14)0.0262 (15)0.0001 (11)
C170.089 (2)0.071 (2)0.0360 (14)−0.053 (2)0.0204 (16)−0.0103 (14)
C180.0436 (12)0.0350 (11)0.0307 (11)0.0006 (10)0.0179 (10)−0.0003 (9)
C190.0249 (9)0.0289 (10)0.0242 (10)0.0005 (8)0.0080 (8)−0.0015 (8)
C200.0406 (12)0.0276 (11)0.0617 (16)0.0050 (10)0.0261 (12)0.0003 (11)
C210.0271 (10)0.0223 (9)0.0484 (13)−0.0001 (8)0.0179 (10)0.0013 (9)
C220.0332 (12)0.0383 (12)0.0450 (14)−0.0049 (10)0.0123 (11)0.0063 (11)
C230.0282 (12)0.0508 (15)0.0623 (18)−0.0053 (11)0.0116 (12)0.0077 (13)
C240.0316 (12)0.0470 (14)0.077 (2)−0.0034 (11)0.0282 (13)0.0031 (14)
C250.0407 (13)0.0375 (12)0.0617 (16)−0.0055 (10)0.0320 (13)−0.0044 (12)
C260.0310 (11)0.0244 (9)0.0477 (13)−0.0018 (8)0.0182 (10)−0.0021 (9)
C270.0515 (15)0.0427 (13)0.0443 (14)−0.0125 (12)0.0221 (12)−0.0076 (11)
Geometric parameters (Å, º) top
Br—C141.901 (2)C12—C131.388 (3)
O1—C191.232 (3)C12—H12A0.9500
N1—C81.373 (3)C13—C141.389 (3)
N1—C21.379 (3)C13—C191.510 (3)
N1—C11.456 (3)C15—C181.526 (3)
N2—C81.310 (3)C15—C171.527 (3)
N2—C71.391 (3)C15—C161.545 (4)
N3—C261.365 (3)C16—H16A0.9800
N3—C271.447 (3)C16—H16B0.9800
N3—H3B0.81 (3)C16—H16C0.9800
N4—C191.340 (3)C17—H17A0.9800
N4—C211.450 (3)C17—H17B0.9800
N4—C201.467 (3)C17—H17C0.9800
C1—H1A0.9800C18—H18A0.9800
C1—H1B0.9800C18—H18B0.9800
C1—H1C0.9800C18—H18C0.9800
C2—C71.394 (4)C20—H20A0.9800
C2—C31.401 (4)C20—H20B0.9800
C3—C41.388 (5)C20—H20C0.9800
C3—H3A0.9500C21—C221.383 (3)
C4—C51.395 (5)C21—C261.406 (3)
C4—H4A0.9500C22—C231.387 (3)
C5—C61.376 (5)C22—H22A0.9500
C5—H5A0.9500C23—C241.379 (4)
C6—C71.412 (4)C23—H23A0.9500
C6—H6A0.9500C24—C251.375 (4)
C8—C91.484 (3)C24—H24A0.9500
C9—C141.393 (3)C25—C261.414 (3)
C9—C101.395 (3)C25—H25A0.9500
C10—C111.395 (3)C27—H27A0.9800
C10—H10A0.9500C27—H27B0.9800
C11—C121.396 (3)C27—H27C0.9800
C11—C151.531 (3)
C8—N1—C2106.0 (2)C18—C15—C11111.07 (18)
C8—N1—C1128.4 (2)C17—C15—C11108.6 (2)
C2—N1—C1125.5 (2)C18—C15—C16108.3 (2)
C8—N2—C7104.4 (2)C17—C15—C16109.0 (3)
C26—N3—C27122.4 (2)C11—C15—C16110.6 (2)
C26—N3—H3B117 (2)C15—C16—H16A109.5
C27—N3—H3B119 (2)C15—C16—H16B109.5
C19—N4—C21123.86 (18)H16A—C16—H16B109.5
C19—N4—C20119.04 (18)C15—C16—H16C109.5
C21—N4—C20117.02 (18)H16A—C16—H16C109.5
N1—C1—H1A109.5H16B—C16—H16C109.5
N1—C1—H1B109.5C15—C17—H17A109.5
H1A—C1—H1B109.5C15—C17—H17B109.5
N1—C1—H1C109.5H17A—C17—H17B109.5
H1A—C1—H1C109.5C15—C17—H17C109.5
H1B—C1—H1C109.5H17A—C17—H17C109.5
N1—C2—C7105.7 (2)H17B—C17—H17C109.5
N1—C2—C3131.4 (3)C15—C18—H18A109.5
C7—C2—C3123.0 (3)C15—C18—H18B109.5
C4—C3—C2115.7 (3)H18A—C18—H18B109.5
C4—C3—H3A122.1C15—C18—H18C109.5
C2—C3—H3A122.1H18A—C18—H18C109.5
C3—C4—C5122.0 (3)H18B—C18—H18C109.5
C3—C4—H4A119.0O1—C19—N4122.7 (2)
C5—C4—H4A119.0O1—C19—C13119.92 (19)
C6—C5—C4122.0 (3)N4—C19—C13117.37 (17)
C6—C5—H5A119.0N4—C20—H20A109.5
C4—C5—H5A119.0N4—C20—H20B109.5
C5—C6—C7117.2 (3)H20A—C20—H20B109.5
C5—C6—H6A121.4N4—C20—H20C109.5
C7—C6—H6A121.4H20A—C20—H20C109.5
N2—C7—C2110.2 (2)H20B—C20—H20C109.5
N2—C7—C6129.8 (3)C22—C21—C26121.5 (2)
C2—C7—C6120.0 (3)C22—C21—N4119.1 (2)
N2—C8—N1113.7 (2)C26—C21—N4119.1 (2)
N2—C8—C9124.9 (2)C21—C22—C23120.3 (3)
N1—C8—C9121.4 (2)C21—C22—H22A119.8
C14—C9—C10118.6 (2)C23—C22—H22A119.8
C14—C9—C8122.40 (19)C24—C23—C22119.0 (3)
C10—C9—C8119.00 (19)C24—C23—H23A120.5
C9—C10—C11121.9 (2)C22—C23—H23A120.5
C9—C10—H10A119.0C25—C24—C23121.4 (2)
C11—C10—H10A119.0C25—C24—H24A119.3
C10—C11—C12117.3 (2)C23—C24—H24A119.3
C10—C11—C15121.96 (19)C24—C25—C26120.8 (3)
C12—C11—C15120.7 (2)C24—C25—H25A119.6
C13—C12—C11122.3 (2)C26—C25—H25A119.6
C13—C12—H12A118.8N3—C26—C21121.4 (2)
C11—C12—H12A118.8N3—C26—C25121.8 (2)
C12—C13—C14118.62 (19)C21—C26—C25116.8 (2)
C12—C13—C19119.05 (19)N3—C27—H27A109.5
C14—C13—C19122.21 (19)N3—C27—H27B109.5
C13—C14—C9121.17 (19)H27A—C27—H27B109.5
C13—C14—Br119.78 (16)N3—C27—H27C109.5
C9—C14—Br119.01 (16)H27A—C27—H27C109.5
C18—C15—C17109.2 (2)H27B—C27—H27C109.5
C8—N1—C2—C70.1 (2)C12—C13—C14—Br−177.74 (14)
C1—N1—C2—C7177.6 (2)C19—C13—C14—Br−1.6 (3)
C8—N1—C2—C3178.1 (3)C10—C9—C14—C130.4 (3)
C1—N1—C2—C3−4.3 (4)C8—C9—C14—C13179.08 (19)
N1—C2—C3—C4−176.7 (3)C10—C9—C14—Br178.12 (15)
C7—C2—C3—C41.0 (4)C8—C9—C14—Br−3.2 (3)
C2—C3—C4—C5−2.2 (4)C10—C11—C15—C18−154.3 (2)
C3—C4—C5—C61.9 (5)C12—C11—C15—C1826.3 (3)
C4—C5—C6—C7−0.2 (5)C10—C11—C15—C1785.6 (3)
C8—N2—C7—C2−0.3 (3)C12—C11—C15—C17−93.8 (3)
C8—N2—C7—C6−178.8 (3)C10—C11—C15—C16−34.1 (3)
N1—C2—C7—N20.1 (3)C12—C11—C15—C16146.5 (2)
C3—C2—C7—N2−178.1 (2)C21—N4—C19—O1−177.7 (2)
N1—C2—C7—C6178.7 (2)C20—N4—C19—O15.7 (3)
C3—C2—C7—C60.5 (4)C21—N4—C19—C131.1 (3)
C5—C6—C7—N2177.4 (3)C20—N4—C19—C13−175.5 (2)
C5—C6—C7—C2−0.9 (4)C12—C13—C19—O182.7 (3)
C7—N2—C8—N10.4 (3)C14—C13—C19—O1−93.4 (2)
C7—N2—C8—C9177.9 (2)C12—C13—C19—N4−96.1 (2)
C2—N1—C8—N2−0.3 (3)C14—C13—C19—N487.7 (2)
C1—N1—C8—N2−177.8 (2)C19—N4—C21—C22−98.6 (3)
C2—N1—C8—C9−177.9 (2)C20—N4—C21—C2278.2 (3)
C1—N1—C8—C94.6 (4)C19—N4—C21—C2687.6 (3)
N2—C8—C9—C14112.4 (3)C20—N4—C21—C26−95.7 (3)
N1—C8—C9—C14−70.3 (3)C26—C21—C22—C23−2.4 (4)
N2—C8—C9—C10−68.9 (3)N4—C21—C22—C23−176.1 (2)
N1—C8—C9—C10108.4 (2)C21—C22—C23—C240.8 (4)
C14—C9—C10—C110.4 (3)C22—C23—C24—C250.4 (4)
C8—C9—C10—C11−178.28 (19)C23—C24—C25—C260.1 (4)
C9—C10—C11—C12−1.6 (3)C27—N3—C26—C21−177.6 (2)
C9—C10—C11—C15179.03 (19)C27—N3—C26—C254.3 (4)
C10—C11—C12—C132.0 (3)C22—C21—C26—N3−175.4 (2)
C15—C11—C12—C13−178.63 (19)N4—C21—C26—N3−1.7 (3)
C11—C12—C13—C14−1.2 (3)C22—C21—C26—C252.8 (3)
C11—C12—C13—C19−177.46 (18)N4—C21—C26—C25176.5 (2)
C12—C13—C14—C90.0 (3)C24—C25—C26—N3176.5 (2)
C19—C13—C14—C9176.10 (18)C24—C25—C26—C21−1.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1i0.81 (3)2.35 (3)3.038 (3)143 (3)
C4—H4A···Brii0.952.983.719 (3)135
C12—H12A···O1i0.952.373.287 (3)163
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1i0.81 (3)2.35 (3)3.038 (3)143 (3)
C4—H4A···Brii0.952.983.719 (3)135.2
C12—H12A···O1i0.952.373.287 (3)163.3
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+3/2.
 

Acknowledgements

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

First citationAgilent (2012). CrysalisAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.  Google Scholar
 First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CSD CrossRef Web of Science Google Scholar
 First citationBusacca, C. A., Grossbach, D., So, R. C., O'Brien, E. M. & Spinelli, E. M. (2003). Org. Lett. 5, 595–598.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationField, J. E., Hill, T. J. & Venkataraman, D. J. (2003). J. Org. Chem. 68, 6071–6078.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationReddy, K. R. & Krishna, G. G. (2005). Tetrahedron Lett. 46, 661–663.  Web of Science CrossRef CAS Google Scholar
 First citationSelander, N. J. & Szabó, K. (2011). Chem. Rev. 111, 2048–2076.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 7| July 2014| Pages o822-o823
https://doi.org/10.1107/S1600536814014433
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS