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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 11| November 2009| Page o2777
https://doi.org/10.1107/S1600536809040112

4-Bromo-N,N′-bis­­(4-meth­oxy­phen­yl)benzamidine

Amlan K. Pala* and Garry S. Hanana

aDépartement de Chimie, Université de Montréal, CP 6128, Succ. Centre-ville, Montréal, Québec, Canada H3C 3J7
*Correspondence e-mail: amlan.kumar.pal@umontreal.ca

(Received 19 August 2009; accepted 1 October 2009; online 17 October 2009)

The title compound, C21H19BrN2O2, is an amidine containing electron-donating meth­oxy groups and a bulky Br atom on the benzene rings. The solid-state structure reveals a non-centrosymmetric mol­ecule, with an E configuration around the C=N double bond. The C—N bonds show distinct amine [1.3689 (19) Å] and imine [1.285 (2) Å] characteristics. In the crystal, symmetry-related mol­ecules are linked via a very weak N—H⋯N inter­action, and C—H⋯O and C—H⋯π inter­actions.

Related literature

For the use of benzamidine ligands as dimetallic tetra­midinate complexes, see: Chartrand & Hanan (2008[Chartrand, D. & Hanan, G. (2008). Chem. Commun. pp. 727-729.]). For structural features of this kind of benzamidine ligand, see: Alcock et al. (1988[Alcock, N. W., Barker, J. & Kilner, M. (1988). Acta Cryst. C44, 712-715.], 1994[Alcock, N. W., Blacker, N. C., Errington, W., Wallbridge, M. G. H. & Barker, J. (1994). Acta Cryst. C50, 456-458.]), Bortoluzzi et al. (2004[Bortoluzzi, A. J., Echevarria, A. & Rodrigues-Santos, C. E. (2004). Acta Cryst. E60, o1837-o1839.]), Barker et al. (1999[Barker, J., Errington, W. & Wallbridge, M. G. H. (1999). Acta Cryst. C55, 1583-1585.]). For structural features of acetamidine and formamidine ligands see: Norrestam et al. (1983[Norrestam, R., Mertz, S. & Crossland, I. (1983). Acta Cryst. C39, 1554-1556.]); Cotton et al. (1997[Cotton, F. A., Haefner, S. C., Matonic, J. H., Wang, X. & Murillo, C. A. (1997). Polyhedron, 16, 541-550.]).

[Scheme 1]

Experimental

Crystal data

  • C21H19BrN2O2

  • Mr = 411.29

  • Orthorhombic, P b c a

  • a = 9.2582 (6) Å

  • b = 16.8837 (10) Å

  • c = 23.9403 (14) Å

  • V = 3742.2 (4) Å3

  • Z = 8

  • Cu Kα radiation

  • μ = 3.13 mm−1

  • T = 150 K

  • 0.14 × 0.14 × 0.03 mm
Data collection

  • Bruker Microstar diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.610, Tmax = 0.910

  • 52443 measured reflections

  • 3396 independent reflections

  • 3299 reflections with I > 2σ(I)

  • Rint = 0.062
Refinement

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.080

  • S = 1.07

  • 3396 reflections

  • 237 parameters

  • H-atom parameters constrained

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.59 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯N2i 0.88 2.70 3.478 (2) 149
C14—H14B⋯O2ii 0.98 2.43 3.327 (2) 151
C7—H7⋯Cg2iii 0.95 2.67 3.3282 (18) 127
C13—H13⋯Cg3iii 0.95 2.69 3.6307 (17) 171
Symmetry codes: (i) [x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]; (iii) [x-{\script{1\over 2}}, y, -z-{\script{1\over 2}}]. Cg2 and Cg3 are the centroids of the C8–C13 and C15–C20 rings, respectively.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: UdMX (Maris, 2004[Maris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809040112/su2139sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040112/su2139Isup2.hkl

checkCIF report


Comment top

Benzamidine ligands are of immense importance as amidinate complexes with dimetallic units (like Rh, Mo) can act as chromophores in light-harvesting devices (Chartrand & Hanan, 2008).

The title compound (Fig. 1) is an amidine containing electron donating methoxy groups on phenyl rings A and C, and a bulky bromine atom on phenyl ring B. Motives like these are of interest due to the fact that they can be incorporated into supramolecular assemblies via coordination chemistry. The C-N bonds show distinct amine [1.3689 (19) Å for C1-N1] and imine [1.285 (2) Å for C1═N2] characteristics, which on complexation become near equivalent bonds with a higher degree of delocalization. These values are similar to the values found in N,N'-diphenylbenzamidine [1.302 (7) Å and 1.360 (8) Å, respectively](Alcock et al., 1988) and 4-methoxy-N,N'-diphenylbenzamidine [1.283 (2) Å and 1.372 (2) Å, respectively] (Bortoluzzi et al., 2004), but differ to those found in N,N'-diphenylbenzamidinium nitrate [1.3266 (18) Å ] (Barker et al., 1999).

It is already known that the difference between C-N and C═N depends on the degree of delocalisation in the N-C═N skeleton. In the title compound the difference is 0.0839 Å, whereas it is 0.058 Å in N,N'-diphenylbenzamidine (Alcock et al., 1988), 0.046 Å in acetamidine (Norrestam and Mertz, 1983), and 0.06 Å in N,N'-di(p-tolyl)benzamidine (Alcock et al., 1994). This correlation clearly proves that the degree of delocalisation depends on the substituents on the phenyl rings. In the title compound the bromine atom and the methoxy groups strongly influence the N-C═N congugation (0.0839 Å), in comparison with the unsubstituted compound N,N'-diphenylbenzamidine (0.058 Å).

From the torsion angles, C8-N1-C1-N2 = 13.9 (3)° and C8-N1-C1-C2 = 166.9 (14)°, it is revealed that the H-atom, H1, along with atom N1 and the phenyl substituent (ring A) at N2 are in an E (trans) configuration with respect to the C1═N2 bond. The solid state structure of the title compound indicates that the imine lone pair and the N1-H1 bond are on opposite sides of the molecule. This orientation hinders self association to give cyclic dimer formation, as observed in N,N'-di(p-chlorophenyl)formamidine (Cotton et al., 1997). The widening of the N1-C1-N2 bond angle [121.89 (14)°] and the slight deviation from the ideal sp2 bond angle (120°), also observed in N,N'-diphenylbenzamidine (120.4°) and N,N'-di(p-tolyl)benzamidine (120.8), is assumed to be due to intermolecular interactions.

In the crystal symmetry related molecules are linked by a very weak N-H···N, interaction and by C-H···O and C-H···π interactions (see Table 1 for details).

Related literature top

For the use of benzamidine ligands as dimetallic tetramidinate complexes, see: Chartrand et al. (2008). For structural features of this kind of benzamidine ligand, see: Alcock et al. (1988, 1994), Bortoluzzi et al. (2004), Barker et al. (1999). For structural features of acetamidine and formamidine ligands see: Norrestam et al. (1983); Cotton et al. (1997). Cg2 and Cg3 are the centroids of the C8–C13 and C15–C20 rings, respectively.

Experimental top

The title compound was prepared according to following procedure. A 250 ml round-bottomed flask was charged with p-bromobenzoic acid (10.0 g, 49.0 mmol) and SOCl2(45 ml). The resulting slurry was refluxed under a N2 atmosphere for 2 h to give a clear solution. The solution was cooled to rt and the unreacted SOCl2 was removed by distillation. The residue was then dried for 2 h under vacuum to give colourless crystalline p-bromobenzoyl chloride (11.0 g, 100%). Dry DCM (60 ml) and dry Et3N (20 ml, 143 mmol) were added to the residue at 283 K under a N2 atmosphere to give a brown precipitate. A solution of p-anisidine (7.0 g, 56 mmol) in another aliquot of dry DCM (40 ml) was then added to the reaction mixture over 30 min by syringe at 283 K to give a pale brown precipitate. The flask was then fitted with a reflux condenser and the slurry was heated to reflux for 10 h and a yellowish brown precipitate formed. After 10 h the mixture was cooled to rt and then evaporated to dryness to give a yellowish brown residue. Distilled water (200 ml) was then added and the resulting slurry was filtered and the solid rinsed with methanol (3 × 100 ml) to give colourless spongy crystalline 4-bromo-4'-methoxybenzanilide (15 g, 98%). (2) To a stirred solution of 4-bromo-4'-methoxybenzanilide (4.0 g, 13 mmol) in dry DCM (40 ml), in a 250 ml round-bottomed flask, was added a solution of PCl5 (5.0 g, 24 mmol) in dry DCM (30 ml) by a syringe at 283 K under a N2 atmosphere. The resulting slurry was then allowed to come to rt and was stirred for 2 h to give a clear bright yellow solution. After 2 h a solution of p-anisidine (4.8 g, 39 mmol) in another aliquot of dry DCM (30 ml) was added with stirring under a N2 atmosphere, maintaining the temperature at 283 K, and then the solution was allowed to reach rt. This solution was then stirred at rt for 1 h, giving pale yellow precipitate, and then was evaporated to dryness yielding a pale yellow residue, which was poured into a beaker containing basic aqueous KOH solution (200 ml, pH>12) to give an off-yellow residue. This residue was then filtered off and rinsed with water (5 × 100 ml) and dried under vacuum. Slow evaporation of an EtOAc solution of this pale-yellow solid gave pale-yellow crystals of the title compound (4.6 g, 85%). Colourless crystalline plates, suitable for X-ray analysis, were obtained by slow evaporation of a concentrated EtOAc solution of the title compound.

1H NMR (DMSO-d6,400 MHz, 330 K): d 8.97 (b, s, 1H), 7.76 (b, s, 2H), 7.52 (d, J = 8 Hz, 2H), 7.21 (d, J = 8 Hz, 2H), 6.85 (b, s, 2H), 6.62 (b, s, 2H), 6.49 (b, s, 2H), 3.66 (d, J = 37 Hz, 6H) p.p.m. Elemental analysis: expected for C21H19N2O2Br; C = 61.33%, H = 4.66%, N = 6.81%; found: C = 61.04%, H = 4.57%, N = 6.75%.

Refinement top

The H-atoms were included in calculated positions and treated as riding atoms: amine N—H 0.88 Å, aromatic C—H 0.95 Å, methyl C—H 0.98 Å, with Uiso(H) = k × Ueq(parent N- or C-atom), where k = 1.2 for the amine and aromatic H-atoms and 1.5 for the methyl H-atoms.

Structure description top

Benzamidine ligands are of immense importance as amidinate complexes with dimetallic units (like Rh, Mo) can act as chromophores in light-harvesting devices (Chartrand & Hanan, 2008).

The title compound (Fig. 1) is an amidine containing electron donating methoxy groups on phenyl rings A and C, and a bulky bromine atom on phenyl ring B. Motives like these are of interest due to the fact that they can be incorporated into supramolecular assemblies via coordination chemistry. The C-N bonds show distinct amine [1.3689 (19) Å for C1-N1] and imine [1.285 (2) Å for C1═N2] characteristics, which on complexation become near equivalent bonds with a higher degree of delocalization. These values are similar to the values found in N,N'-diphenylbenzamidine [1.302 (7) Å and 1.360 (8) Å, respectively](Alcock et al., 1988) and 4-methoxy-N,N'-diphenylbenzamidine [1.283 (2) Å and 1.372 (2) Å, respectively] (Bortoluzzi et al., 2004), but differ to those found in N,N'-diphenylbenzamidinium nitrate [1.3266 (18) Å ] (Barker et al., 1999).

It is already known that the difference between C-N and C═N depends on the degree of delocalisation in the N-C═N skeleton. In the title compound the difference is 0.0839 Å, whereas it is 0.058 Å in N,N'-diphenylbenzamidine (Alcock et al., 1988), 0.046 Å in acetamidine (Norrestam and Mertz, 1983), and 0.06 Å in N,N'-di(p-tolyl)benzamidine (Alcock et al., 1994). This correlation clearly proves that the degree of delocalisation depends on the substituents on the phenyl rings. In the title compound the bromine atom and the methoxy groups strongly influence the N-C═N congugation (0.0839 Å), in comparison with the unsubstituted compound N,N'-diphenylbenzamidine (0.058 Å).

From the torsion angles, C8-N1-C1-N2 = 13.9 (3)° and C8-N1-C1-C2 = 166.9 (14)°, it is revealed that the H-atom, H1, along with atom N1 and the phenyl substituent (ring A) at N2 are in an E (trans) configuration with respect to the C1═N2 bond. The solid state structure of the title compound indicates that the imine lone pair and the N1-H1 bond are on opposite sides of the molecule. This orientation hinders self association to give cyclic dimer formation, as observed in N,N'-di(p-chlorophenyl)formamidine (Cotton et al., 1997). The widening of the N1-C1-N2 bond angle [121.89 (14)°] and the slight deviation from the ideal sp2 bond angle (120°), also observed in N,N'-diphenylbenzamidine (120.4°) and N,N'-di(p-tolyl)benzamidine (120.8), is assumed to be due to intermolecular interactions.

In the crystal symmetry related molecules are linked by a very weak N-H···N, interaction and by C-H···O and C-H···π interactions (see Table 1 for details).

For the use of benzamidine ligands as dimetallic tetramidinate complexes, see: Chartrand et al. (2008). For structural features of this kind of benzamidine ligand, see: Alcock et al. (1988, 1994), Bortoluzzi et al. (2004), Barker et al. (1999). For structural features of acetamidine and formamidine ligands see: Norrestam et al. (1983); Cotton et al. (1997). Cg2 and Cg3 are the centroids of the C8–C13 and C15–C20 rings, respectively.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: UdMX (Maris, 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the numbering scheme and displacement ellipsoids drawn at the 50% probability level.
4-Bromo-N,N'-bis(4-methoxyphenyl)benzamidine top
Crystal data top
C21H19BrN2O2F(000) = 1680
Mr = 411.29Dx = 1.460 Mg m−3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2abCell parameters from 36728 reflections
a = 9.2582 (6) Åθ = 4.8–67.9°
b = 16.8837 (10) ŵ = 3.13 mm−1
c = 23.9403 (14) ÅT = 150 K
V = 3742.2 (4) Å3Plate, colorless
Z = 80.14 × 0.14 × 0.03 mm
Data collection top
Bruker Microstar
diffractometer		3396 independent reflections
Radiation source: Rotating Anode3299 reflections with I > 2σ(I)
Helios optics monochromatorRint = 0.062
Detector resolution: 8.3 pixels mm-1θmax = 68.1°, θmin = 5.2°
ω scansh = −11→9
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		k = −19→20
Tmin = 0.610, Tmax = 0.910l = −28→28
52443 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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0478P)2 + 1.6131P]
where P = (Fo2 + 2Fc2)/3
3396 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.59 e Å−3
Crystal data top
C21H19BrN2O2V = 3742.2 (4) Å3
Mr = 411.29Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 9.2582 (6) ŵ = 3.13 mm−1
b = 16.8837 (10) ÅT = 150 K
c = 23.9403 (14) Å0.14 × 0.14 × 0.03 mm
Data collection top
Bruker Microstar
diffractometer		3396 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		3299 reflections with I > 2σ(I)
Tmin = 0.610, Tmax = 0.910Rint = 0.062
52443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 1.07Δρmax = 0.33 e Å−3
3396 reflectionsΔρmin = −0.59 e Å−3
237 parameters
Special details top

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker microstar diffractometer equiped with a Platinum 135 CCD Detector, a Helios optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over three different parts of the reciprocal space (99 frames total).

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
Br11.11149 (2)0.899798 (11)0.150666 (8)0.03899 (10)
O10.40209 (14)0.43856 (8)0.43426 (5)0.0390 (3)
O20.40707 (14)0.73586 (8)−0.00500 (5)0.0394 (3)
N10.72340 (15)0.60992 (8)0.27898 (5)0.0276 (3)
H10.80630.62590.29300.033*
N20.59343 (16)0.60447 (8)0.19620 (6)0.0306 (3)
C10.69482 (16)0.63517 (9)0.22578 (6)0.0252 (3)
C20.79459 (16)0.69987 (9)0.20695 (6)0.0248 (3)
C30.80061 (17)0.77121 (9)0.23594 (6)0.0296 (3)
H30.74070.77890.26770.035*
C40.89304 (17)0.83133 (10)0.21905 (7)0.0318 (4)
H40.89630.88020.23870.038*
C50.98037 (17)0.81875 (9)0.17299 (7)0.0285 (3)
C60.97609 (18)0.74872 (10)0.14314 (7)0.0297 (3)
H61.03650.74120.11150.036*
C70.88162 (17)0.68942 (10)0.16033 (7)0.0269 (3)
H70.87670.64120.13990.032*
C80.63946 (17)0.56199 (9)0.31467 (6)0.0245 (3)
C90.52398 (17)0.51543 (9)0.29732 (6)0.0266 (3)
H90.50040.51250.25880.032*
C100.44259 (18)0.47305 (9)0.33623 (7)0.0288 (3)
H100.36370.44150.32400.035*
C110.47627 (17)0.47678 (9)0.39259 (7)0.0284 (3)
C120.59362 (18)0.52215 (10)0.41022 (7)0.0292 (3)
H120.61820.52420.44870.035*
C130.67413 (17)0.56419 (9)0.37168 (7)0.0270 (3)
H130.75400.59500.38400.032*
C140.2813 (2)0.39151 (11)0.41797 (9)0.0407 (4)
H14A0.20950.42510.39940.061*
H14B0.23790.36710.45110.061*
H14C0.31330.35000.39220.061*
C150.55222 (17)0.64111 (10)0.14555 (6)0.0274 (3)
C160.49751 (18)0.71759 (10)0.14424 (6)0.0295 (3)
H160.49560.74790.17770.035*
C170.44532 (19)0.75103 (10)0.09498 (6)0.0309 (4)
H170.40660.80310.09510.037*
C180.45031 (17)0.70775 (10)0.04598 (6)0.0305 (3)
C190.50326 (18)0.63055 (10)0.04669 (6)0.0313 (4)
H190.50540.60050.01320.038*
C200.55266 (19)0.59746 (9)0.09586 (7)0.0305 (4)
H200.58730.54450.09600.037*
C210.3394 (3)0.81124 (14)−0.00580 (8)0.0532 (5)
H21A0.25660.81100.01970.080*
H21B0.30610.8230−0.04380.080*
H21C0.40860.85180.00610.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03179 (15)0.02995 (14)0.05522 (16)−0.00738 (7)0.00078 (7)0.01143 (7)
O10.0405 (7)0.0416 (7)0.0348 (6)−0.0134 (5)0.0058 (5)0.0085 (5)
O20.0449 (7)0.0458 (7)0.0275 (6)−0.0014 (6)−0.0100 (5)0.0050 (5)
N10.0228 (7)0.0332 (7)0.0268 (6)−0.0063 (5)−0.0028 (5)0.0050 (5)
N20.0293 (7)0.0358 (8)0.0268 (7)−0.0084 (5)−0.0012 (6)0.0049 (5)
C10.0225 (7)0.0276 (8)0.0256 (7)−0.0012 (6)0.0017 (6)0.0018 (6)
C20.0210 (7)0.0272 (7)0.0262 (7)−0.0007 (6)−0.0033 (6)0.0036 (6)
C30.0278 (8)0.0323 (8)0.0287 (7)−0.0015 (7)0.0017 (6)−0.0016 (6)
C40.0329 (9)0.0270 (8)0.0357 (9)−0.0027 (6)−0.0027 (6)−0.0023 (7)
C50.0232 (7)0.0259 (8)0.0365 (8)−0.0026 (6)−0.0039 (6)0.0082 (6)
C60.0267 (8)0.0315 (8)0.0310 (8)0.0013 (7)0.0038 (6)0.0056 (6)
C70.0266 (8)0.0256 (8)0.0284 (7)0.0010 (6)−0.0004 (6)0.0022 (6)
C80.0223 (7)0.0245 (7)0.0266 (7)0.0008 (6)0.0010 (6)0.0026 (6)
C90.0277 (8)0.0240 (7)0.0282 (7)−0.0002 (6)−0.0012 (6)0.0000 (6)
C100.0283 (8)0.0232 (7)0.0349 (8)−0.0033 (6)−0.0013 (7)0.0006 (6)
C110.0285 (8)0.0250 (7)0.0318 (8)−0.0015 (6)0.0050 (6)0.0051 (6)
C120.0297 (8)0.0321 (8)0.0257 (7)−0.0012 (6)−0.0015 (6)0.0032 (6)
C130.0222 (8)0.0291 (8)0.0297 (8)−0.0020 (6)−0.0026 (6)0.0018 (6)
C140.0315 (10)0.0351 (9)0.0555 (11)−0.0073 (7)0.0091 (8)0.0081 (8)
C150.0218 (8)0.0353 (9)0.0252 (7)−0.0078 (7)−0.0001 (6)0.0042 (6)
C160.0259 (8)0.0357 (9)0.0268 (7)−0.0033 (7)−0.0001 (6)−0.0035 (6)
C170.0268 (9)0.0339 (9)0.0319 (8)−0.0009 (6)−0.0015 (6)0.0011 (7)
C180.0244 (8)0.0397 (9)0.0275 (8)−0.0064 (7)−0.0026 (6)0.0044 (6)
C190.0313 (8)0.0372 (9)0.0254 (7)−0.0053 (7)0.0001 (6)−0.0028 (6)
C200.0280 (9)0.0319 (9)0.0316 (8)−0.0036 (6)0.0007 (7)−0.0002 (6)
C210.0551 (12)0.0662 (14)0.0383 (10)0.0196 (11)−0.0079 (9)0.0126 (9)
Geometric parameters (Å, º) top
Br1—C51.9057 (15)C9—H90.95
O1—C111.3723 (19)C10—C111.386 (2)
O1—C141.426 (2)C10—H100.95
O2—C181.369 (2)C11—C121.395 (2)
O2—C211.419 (3)C12—C131.382 (2)
N1—C11.3689 (19)C12—H120.95
N1—C81.410 (2)C13—H130.95
N1—H10.88C14—H14a0.98
N2—C11.285 (2)C14—H14b0.98
N2—C151.414 (2)C14—H14c0.98
C1—C21.500 (2)C15—C161.387 (3)
C2—C71.388 (2)C15—C201.399 (2)
C2—C31.391 (2)C16—C171.394 (2)
C3—C41.388 (2)C16—H160.95
C3—H30.95C17—C181.383 (2)
C4—C51.384 (2)C17—H170.95
C4—H40.95C18—C191.393 (2)
C5—C61.382 (2)C19—C201.381 (2)
C6—C71.392 (2)C19—H190.95
C6—H60.95C20—H200.95
C7—H70.95C21—H21a0.98
C8—C91.390 (2)C21—H21b0.98
C8—C131.403 (2)C21—H21c0.98
C9—C101.396 (2)
C11—O1—C14117.11 (14)C10—C11—C12119.65 (14)
C18—O2—C21116.88 (14)C13—C12—C11120.01 (15)
C1—N1—C8129.49 (13)C13—C12—H12120
C1—N1—H1115.3C11—C12—H12120
C8—N1—H1115.3C12—C13—C8120.83 (14)
C1—N2—C15119.55 (14)C12—C13—H13119.6
N2—C1—N1121.89 (14)C8—C13—H13119.6
N2—C1—C2125.31 (14)O1—C14—H14A109.5
N1—C1—C2112.80 (13)O1—C14—H14B109.5
C7—C2—C3119.20 (14)H14A—C14—H14B109.5
C7—C2—C1120.45 (14)O1—C14—H14C109.5
C3—C2—C1120.35 (14)H14A—C14—H14C109.5
C4—C3—C2120.83 (15)H14B—C14—H14C109.5
C4—C3—H3119.6C16—C15—C20118.17 (14)
C2—C3—H3119.6C16—C15—N2121.68 (14)
C5—C4—C3118.70 (15)C20—C15—N2119.86 (16)
C5—C4—H4120.6C15—C16—C17121.51 (15)
C3—C4—H4120.6C15—C16—H16119.2
C6—C5—C4121.78 (15)C17—C16—H16119.2
C6—C5—BR1119.18 (12)C18—C17—C16119.47 (16)
C4—C5—BR1119.04 (12)C18—C17—H17120.3
C5—C6—C7118.73 (15)C16—C17—H17120.3
C5—C6—H6120.6O2—C18—C17124.27 (16)
C7—C6—H6120.6O2—C18—C19115.98 (15)
C2—C7—C6120.74 (15)C17—C18—C19119.74 (15)
C2—C7—H7119.6C20—C19—C18120.37 (15)
C6—C7—H7119.6C20—C19—H19119.8
C9—C8—C13118.79 (14)C18—C19—H19119.8
C9—C8—N1124.55 (14)C19—C20—C15120.70 (15)
C13—C8—N1116.63 (14)C19—C20—H20119.7
C8—C9—C10120.38 (14)C15—C20—H20119.7
C8—C9—H9119.8O2—C21—H21A109.5
C10—C9—H9119.8O2—C21—H21B109.5
C11—C10—C9120.32 (15)H21A—C21—H21B109.5
C11—C10—H10119.8O2—C21—H21C109.5
C9—C10—H10119.8H21A—C21—H21C109.5
O1—C11—C10125.00 (15)H21B—C21—H21C109.5
O1—C11—C12115.35 (14)
C15—N2—C1—N1169.37 (15)C14—O1—C11—C100.0 (2)
C15—N2—C1—C2−11.6 (2)C14—O1—C11—C12180.00 (15)
C8—N1—C1—N2−13.9 (3)C9—C10—C11—O1178.93 (15)
C8—N1—C1—C2166.90 (14)C9—C10—C11—C12−1.1 (2)
N2—C1—C2—C7−58.9 (2)O1—C11—C12—C13−178.87 (15)
N1—C1—C2—C7120.22 (16)C10—C11—C12—C131.1 (2)
N2—C1—C2—C3120.87 (18)C11—C12—C13—C80.0 (2)
N1—C1—C2—C3−59.99 (19)C9—C8—C13—C12−1.2 (2)
C7—C2—C3—C4−0.5 (2)N1—C8—C13—C12176.93 (15)
C1—C2—C3—C4179.68 (14)C1—N2—C15—C16−61.3 (2)
C2—C3—C4—C5−0.6 (2)C1—N2—C15—C20125.04 (17)
C3—C4—C5—C61.0 (2)C20—C15—C16—C17−0.6 (2)
C3—C4—C5—BR1−178.30 (12)N2—C15—C16—C17−174.34 (15)
C4—C5—C6—C7−0.3 (2)C15—C16—C17—C18−1.2 (3)
BR1—C5—C6—C7178.98 (12)C21—O2—C18—C17−6.8 (2)
C3—C2—C7—C61.2 (2)C21—O2—C18—C19173.81 (17)
C1—C2—C7—C6−178.98 (14)C16—C17—C18—O2−177.47 (15)
C5—C6—C7—C2−0.8 (2)C16—C17—C18—C191.9 (2)
C1—N1—C8—C916.0 (3)O2—C18—C19—C20178.51 (15)
C1—N1—C8—C13−162.04 (15)C17—C18—C19—C20−0.9 (2)
C13—C8—C9—C101.3 (2)C18—C19—C20—C15−0.9 (3)
N1—C8—C9—C10−176.71 (15)C16—C15—C20—C191.6 (2)
C8—C9—C10—C11−0.2 (2)N2—C15—C20—C19175.47 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.882.703.478 (2)149
C14—H14B···O2ii0.982.433.327 (2)151
C7—H7···Cg2iii0.952.673.3282 (18)127
C13—H13···Cg3iii0.952.693.6307 (17)171
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, y, −z−1/2.

Experimental details

Crystal data
Chemical formulaC21H19BrN2O2
Mr411.29
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)9.2582 (6), 16.8837 (10), 23.9403 (14)
V (Å3)3742.2 (4)
Z8
Radiation typeCu Kα
µ (mm−1)3.13
Crystal size (mm)0.14 × 0.14 × 0.03
Data collection
DiffractometerBruker Microstar
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.610, 0.910
No. of measured, independent and
observed [I > 2σ(I)] reflections		52443, 3396, 3299
Rint0.062
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.080, 1.07
No. of reflections3396
No. of parameters237
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.33, −0.59

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), UdMX (Maris, 2004).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.882.703.478 (2)149
C14—H14B···O2ii0.982.433.327 (2)151
C7—H7···Cg2iii0.952.673.3282 (18)127
C13—H13···Cg3iii0.952.693.6307 (17)171
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, y, −z−1/2.
 

Acknowledgements

We are grateful to the Natural Sciences and Engineering Research Council of Canada and the University of Montreal for financial support.

References

First citationAlcock, N. W., Barker, J. & Kilner, M. (1988). Acta Cryst. C44, 712–715.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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 First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2007). SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
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 First citationCotton, F. A., Haefner, S. C., Matonic, J. H., Wang, X. & Murillo, C. A. (1997). Polyhedron, 16, 541–550.  CSD CrossRef CAS Web of Science Google Scholar
 First citationMaris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada.  Google Scholar
 First citationNorrestam, R., Mertz, S. & Crossland, I. (1983). Acta Cryst. C39, 1554–1556.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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ISSN: 2056-9890
Volume 65| Part 11| November 2009| Page o2777
https://doi.org/10.1107/S1600536809040112
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