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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 o2640
https://doi.org/10.1107/S1600536809039130

N-(2-Bromo­benz­yl)-N′-(2-pyrid­yl)benzene-1,2-di­amine

Sudesh T. Manjare,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: chhbsia@chem.iitb.ac.in

(Received 24 September 2009; accepted 26 September 2009; online 3 October 2009)

In the title compound, C18H16BrN3, mol­ecules are linked into dimers by co-operative inter­molecular N—H⋯N hydrogen bonding. Only one N—H group is involved in hydrogen bonding. The planes of the pyridine and bromo­phenyl rings are twisted by 61.49 (3) and 79.11 (8)°, respectively, from the plane of the central phenyl ring.

Related literature

The title compound was isolated as part of a project to further investigate the chemistry of chalcogen–carbene compounds (Dutton et al., 2007[Dutton, J. L., Tabeshi, R., Jennings, M. C., Logh, A. J. & Ragogna, P. J. (2007). Inorg. Chem. 46, 8594-8602.]). The stability of imidazole-based carbenes depends very much on the nature of the substituents attached to the imidazole nitrogen atoms, see: Huynh et al. (2006[Huynh, H. V., Han, Y., Ho, J. H. H. & Tan, G. K. (2006). Organometallics, 25, 3267-3274.]); Kuhn et al. (1993[Kuhn, N., Henkel, G. & Kratz, T. (1993). Chem. Ber. 126, 2047-2049.]). For bond lengths in analogous compounds, see: Albéniz et al. (2002[Albéniz, A. C., Espinet, P., Manrique, R. & Pérez-Mateo, A. (2002). Angew. Chem. Int. Ed. 41, 2363-2366.]); Denk et al. (2001[Denk, M. K., Rodezno, J. M., Gupta, S. & Lough, L. J. (2001). J. Organomet. Chem. 617, 242-253.]). For details of the synthesis, see: Hahn et al. (2007[Hahn, F. E., Jahnke, M. C. & Pape, T. (2007). Organometallics, 26, 150-154.]).

[Scheme 1]

Experimental

Crystal data

  • C18H16BrN3

  • Mr = 354.25

  • Triclinic, [P \overline 1]

  • a = 7.9429 (5) Å

  • b = 9.5314 (8) Å

  • c = 11.0606 (8) Å

  • α = 98.741 (6)°

  • β = 90.727 (6)°

  • γ = 103.581 (6)°

  • V = 803.48 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.56 mm−1

  • T = 200 K

  • 0.51 × 0.43 × 0.16 mm
Data collection

  • Oxford Diffraction Gemini R diffractometer

  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.553, Tmax = 1.000

  • 8461 measured reflections

  • 3249 independent reflections

  • 2038 reflections with I > 2σ(I)

  • Rint = 0.042
Refinement

  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.092

  • S = 0.89

  • 3249 reflections

  • 199 parameters

  • H-atom parameters constrained

  • Δρmax = 0.59 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H2A⋯N3i 0.88 2.08 2.952 (3) 175
Symmetry code: (i) -x+1, -y, -z.

Data collection: CrysAlis Pro (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039130/bt5071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039130/bt5071Isup2.hkl

checkCIF report


Comment top

The structure of the title compound, C18H16BrN3, (2), is shown below. Dimensions are available in the archived CIF.

Carbene compounds sometimes show unpredictable reactivity patterns and are subject to hydrolysis (Denk et al. 2001; Albéniz et al., 2002). The stability of imidazole based carbenes depends very much on the nature of the substituents attached to the imidazole nitrogen atoms (Hahn et al., 2007; Huynh et al. 2006).

The title compound was isolated as part of a project to further investigate the chemistry of chalcogen-carbene compounds (Dutton et al., 2007), in particular tellurium-carbene chemistry with pyridine as a substituent on the nitrogen of the benzimidazole ring. However, in contrast with electron donating substituents such as n-butyl, and i-propyl, which lead to tellurium carbene formation, electron withdrawing groups such as phenyl and pyridyl result in hydrolysed products, such as the title compound. A repeated attempt to synthesize the pyridine substituted tellurone compound gave the title compound whose structure is reported here.

In (2) the bonds are in the usual ranges found for analogous compounds (Albéniz et al. 2002; Denk et al. 2001)).

The molecules are linked into dimers by cooperative intermolecular N—H···N hydrogen bonding. The two N—H moieties adopt different conformations with respect to the phenyl ring to which they are both attached. N1—H is only twisted by 18.0 (2)° from this plane. As a result of this coplanarity the hydrogen attached to N1 does not form any hydrogen bonds. N2—H, however, is twisted by 51.8 (2)° from this plane so as to participate in the intermolecular hydrogen bonding mentioned above. The planes of the pyridine and bromo-phenyl rings are twisted by 61.49 (3)° and 79.11 (8)° from the plane of the central phenyl ring.

The cleavage of carbene carbon from benzimidazole ring in the title compound may be due to: 1) destabilization of C=Te by the electron withdrawing group present on the benzimidazolium nitrogen, 2) crowding near to the carbene carbon. The exact mechanism is under investigation. This structural study has confirmed the cleavage of the carbene carbon.

Related literature top

For carbene chemistry and structures, see: Albéniz et al. (2002); Denk et al. (2001); Dutton et al. (2007); Hahn et al. (2007); Huynh et al. (2006); Kuhn et al. (1993).

Experimental top

In all cases, the starting benzylimidazoylium salt, 1, shown in scheme (1) was prepared using standard methods (Hahn et al. 2007). With the appropriate salt, the title compound could be made by three different methods: (a). In a round bottom flask the benzylimidazoylium salt 1 (1.0 mmol) was taken in THF (40 mL) under nitrogen atmosphere and of n-BuLi (2.0 mmol) was added at -78 °C, reaction mixture was stirred for 1-2 h. Then Te powder was added to the reaction mixture at room temperature, and stirred for 8-10 h. After completion of reaction, water (30 mL) was added and extracted with dichloromethane, dried over Na2SO4 and evaporated. The residue obtained was dissolved in toluene and small amount of petroleum ether was added to separate the residue from the solution. The solution was filtered, evaporated and the residue was dissolved in diethyl ether and a small amount of petroleum ether (60-80 °C) to afford the pure colorless product in 45% yield.

(b) The benzylimidazoylium salt 1 (1.0 mmol) was added to a brown solution of Na2Te2 (2.0 mmol) at room temperature under nitrogen atmosphere and the reaction mixture was stirred for 6-10 h at room temperature. Then KOtBu (1.0 mmol) was added to the reaction mixture and stirred further for 5-7 h. After completion of reaction, the reaction was quenched by adding water (50 mL), and extracted with dichloromethane, dried over Na2SO4, and evaporated. The residue obtained was dissolved in toluene and small amount of petroleum ether was added to separate the residue from the solution. The solution was filtered and evaporated; the residue was dissolved in diethyl ether and a small amount of petroleum ether (60-80 °C) to afford the pure crystalline product.

(c) In a round bottom flask the benzylimidazoylium salt 1 (1.0 mmol) was taken in THF (40 mL) under nitrogen atmosphere and Te metal powder (1.0 mmol) was added, then KOtBu (2.0 mmol) was added to the reaction mixture at -20 °C. The reaction mixture was stirred for 5-6 h. Then the reaction was quenched by adding water (50 mL), and extracted with dichloromethane, dried over Na2SO4, and evaporated. The residue obtained was dissolved in toluene and some petroleum ether was added to separate the residue from the solution. The solution was filtered and evaporated; the residue was dissolved in diethyl ether and small amount of petroleum ether (60-80 °C) to afford the pure product.

Mp 156-158 °C. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.15 (m, 1H), 7.54 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H), 7.43 (m, 1H), 7.32 (m, 1H), 7.23 (m, 2H), 7.11 (m, 2H), 6.71 (m, 2H), 6.61 (dd, J = 8 Hz, J = 1.2 Hz, 1H), 6.40 (m, 1H), 6.15 (s, 1H), 4.83 (d, J = 5.6 Hz, 1H), 4.41 (d, J = 6 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ (ppm) 158.4, 148.4, 144.5, 138.1, 132.9, 128.9, 128.8, 127.8, 127.6, 127.4, 125.7, 123.4, 117.7, 114.6, 111.7, 107.4, 48.2. MS: m/z 353 [M]+, 355 [M+2]+ . Anal. Calcd. for C18H16BrN3 (%): C, 61.03; H, 4.55; N, 11.86. Found: C, 60.85; H, 4.55; N, 11.40.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.95 and 0.99 Å Uiso(H) = 1.2Ueq(C). The H attached to N was idealized with a distance of 0.88 Å.

Structure description top

The structure of the title compound, C18H16BrN3, (2), is shown below. Dimensions are available in the archived CIF.

Carbene compounds sometimes show unpredictable reactivity patterns and are subject to hydrolysis (Denk et al. 2001; Albéniz et al., 2002). The stability of imidazole based carbenes depends very much on the nature of the substituents attached to the imidazole nitrogen atoms (Hahn et al., 2007; Huynh et al. 2006).

The title compound was isolated as part of a project to further investigate the chemistry of chalcogen-carbene compounds (Dutton et al., 2007), in particular tellurium-carbene chemistry with pyridine as a substituent on the nitrogen of the benzimidazole ring. However, in contrast with electron donating substituents such as n-butyl, and i-propyl, which lead to tellurium carbene formation, electron withdrawing groups such as phenyl and pyridyl result in hydrolysed products, such as the title compound. A repeated attempt to synthesize the pyridine substituted tellurone compound gave the title compound whose structure is reported here.

In (2) the bonds are in the usual ranges found for analogous compounds (Albéniz et al. 2002; Denk et al. 2001)).

The molecules are linked into dimers by cooperative intermolecular N—H···N hydrogen bonding. The two N—H moieties adopt different conformations with respect to the phenyl ring to which they are both attached. N1—H is only twisted by 18.0 (2)° from this plane. As a result of this coplanarity the hydrogen attached to N1 does not form any hydrogen bonds. N2—H, however, is twisted by 51.8 (2)° from this plane so as to participate in the intermolecular hydrogen bonding mentioned above. The planes of the pyridine and bromo-phenyl rings are twisted by 61.49 (3)° and 79.11 (8)° from the plane of the central phenyl ring.

The cleavage of carbene carbon from benzimidazole ring in the title compound may be due to: 1) destabilization of C=Te by the electron withdrawing group present on the benzimidazolium nitrogen, 2) crowding near to the carbene carbon. The exact mechanism is under investigation. This structural study has confirmed the cleavage of the carbene carbon.

For carbene chemistry and structures, see: Albéniz et al. (2002); Denk et al. (2001); Dutton et al. (2007); Hahn et al. (2007); Huynh et al. (2006); Kuhn et al. (1993).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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 molecular structure of C18H16BrN3 the showing the atom numbering scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The molecular packing for C18H16BrN3 viewed down the a axis. The hydrogen bonding between N—H···N is shown by dashed lines.
[Figure 3] Fig. 3. The formation of the title compound.
N-(2-Bromobenzyl)-N'-(2-pyridyl)benzene-1,2-diamine top
Crystal data top
C18H16BrN3Z = 2
Mr = 354.25F(000) = 360
Triclinic, P1Dx = 1.464 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9429 (5) ÅCell parameters from 3047 reflections
b = 9.5314 (8) Åθ = 4.7–34.8°
c = 11.0606 (8) ŵ = 2.56 mm−1
α = 98.741 (6)°T = 200 K
β = 90.727 (6)°Irregular plate, colorless
γ = 103.581 (6)°0.51 × 0.43 × 0.16 mm
V = 803.48 (10) Å3
Data collection top
Oxford Diffraction Gemini R
diffractometer		3249 independent reflections
Radiation source: Enhance (Mo) X-ray Source2038 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 10.5081 pixels mm-1θmax = 26.4°, θmin = 4.7°
ω scansh = −9→9
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −11→11
Tmin = 0.553, Tmax = 1.000l = −13→13
8461 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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.052P)2]
where P = (Fo2 + 2Fc2)/3
3249 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.59 e Å−3
0 restraintsΔρmin = −0.48 e Å−3
Crystal data top
C18H16BrN3γ = 103.581 (6)°
Mr = 354.25V = 803.48 (10) Å3
Triclinic, P1Z = 2
a = 7.9429 (5) ÅMo Kα radiation
b = 9.5314 (8) ŵ = 2.56 mm−1
c = 11.0606 (8) ÅT = 200 K
α = 98.741 (6)°0.51 × 0.43 × 0.16 mm
β = 90.727 (6)°
Data collection top
Oxford Diffraction Gemini R
diffractometer		3249 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		2038 reflections with I > 2σ(I)
Tmin = 0.553, Tmax = 1.000Rint = 0.042
8461 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 0.89Δρmax = 0.59 e Å−3
3249 reflectionsΔρmin = −0.48 e Å−3
199 parameters
Special details top

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
Br0.83487 (5)0.00876 (4)0.69232 (3)0.05856 (16)
N10.7358 (3)0.1251 (3)0.31573 (19)0.0433 (6)
H1A0.67760.05420.25950.052*
N20.5888 (3)0.1863 (3)0.1091 (2)0.0405 (6)
H2A0.61180.10080.08490.049*
N30.3381 (3)0.0980 (2)−0.01114 (19)0.0326 (5)
C10.7931 (4)0.2636 (3)0.2846 (2)0.0351 (7)
C20.7198 (4)0.2970 (3)0.1804 (2)0.0348 (7)
C30.7745 (4)0.4348 (3)0.1484 (3)0.0408 (7)
H3A0.72400.45630.07720.049*
C40.9013 (4)0.5417 (4)0.2185 (3)0.0477 (8)
H4A0.93530.63700.19750.057*
C50.9773 (4)0.5079 (4)0.3189 (3)0.0481 (9)
H5A1.06690.57990.36610.058*
C60.9258 (4)0.3714 (3)0.3522 (2)0.0467 (8)
H6A0.98070.35010.42170.056*
C1A0.7671 (4)0.0915 (3)0.4359 (2)0.0386 (7)
H1AA0.89300.12490.45750.046*
H1AB0.7348−0.01600.43170.046*
C2A0.6705 (3)0.1589 (3)0.5388 (2)0.0342 (7)
C3A0.6902 (4)0.1324 (3)0.6583 (2)0.0384 (7)
C4A0.6043 (4)0.1895 (4)0.7542 (3)0.0487 (9)
H4AA0.61920.16800.83420.058*
C5A0.4973 (5)0.2775 (4)0.7325 (3)0.0563 (10)
H5AA0.43870.31850.79810.068*
C6A0.4744 (4)0.3068 (4)0.6165 (3)0.0546 (9)
H6AA0.39920.36720.60180.066*
C7A0.5616 (4)0.2476 (3)0.5202 (3)0.0441 (8)
H7AA0.54560.26900.44030.053*
C1B0.4294 (4)0.2041 (3)0.0757 (2)0.0343 (7)
C2B0.3615 (4)0.3199 (3)0.1284 (3)0.0434 (8)
H2BA0.42780.39430.18920.052*
C3B0.1994 (4)0.3253 (4)0.0920 (3)0.0492 (8)
H3BA0.15090.40290.12820.059*
C4B0.1052 (4)0.2177 (4)0.0020 (3)0.0495 (8)
H4BA−0.00760.2202−0.02580.059*
C5B0.1800 (4)0.1081 (4)−0.0453 (3)0.0416 (7)
H5BA0.11550.0336−0.10680.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0621 (3)0.0737 (3)0.0418 (2)0.01693 (18)−0.00365 (15)0.01454 (16)
N10.0608 (17)0.0325 (16)0.0236 (12)−0.0093 (12)−0.0039 (11)−0.0031 (10)
N20.0443 (15)0.0301 (15)0.0423 (13)0.0096 (12)−0.0114 (12)−0.0092 (11)
N30.0360 (14)0.0304 (14)0.0282 (12)0.0038 (10)−0.0026 (10)0.0016 (10)
C10.0394 (17)0.0335 (18)0.0242 (14)−0.0033 (13)0.0026 (12)−0.0020 (12)
C20.0414 (17)0.0313 (18)0.0255 (14)0.0038 (13)−0.0022 (12)−0.0071 (12)
C30.0469 (18)0.037 (2)0.0376 (16)0.0091 (15)0.0018 (14)0.0042 (14)
C40.056 (2)0.036 (2)0.0449 (18)0.0000 (15)0.0111 (16)0.0032 (14)
C50.052 (2)0.042 (2)0.0337 (16)−0.0149 (15)0.0044 (15)−0.0058 (14)
C60.052 (2)0.050 (2)0.0245 (14)−0.0113 (16)−0.0044 (13)−0.0005 (14)
C1A0.0429 (18)0.0388 (19)0.0280 (14)−0.0001 (13)0.0022 (12)0.0020 (12)
C2A0.0305 (16)0.0300 (17)0.0330 (15)−0.0077 (13)0.0005 (12)0.0001 (12)
C3A0.0389 (17)0.0340 (18)0.0325 (15)−0.0070 (13)0.0020 (13)0.0000 (12)
C4A0.055 (2)0.046 (2)0.0322 (16)−0.0092 (17)0.0068 (15)−0.0018 (14)
C5A0.060 (2)0.040 (2)0.060 (2)0.0016 (18)0.0256 (18)−0.0052 (17)
C6A0.051 (2)0.041 (2)0.072 (2)0.0117 (16)0.0156 (18)0.0075 (17)
C7A0.0418 (18)0.037 (2)0.0497 (18)0.0007 (15)0.0040 (14)0.0094 (14)
C1B0.0397 (17)0.0336 (18)0.0284 (14)0.0055 (13)0.0060 (13)0.0058 (12)
C2B0.052 (2)0.0335 (19)0.0420 (17)0.0080 (15)0.0057 (15)−0.0006 (13)
C3B0.054 (2)0.042 (2)0.058 (2)0.0196 (17)0.0179 (17)0.0119 (16)
C4B0.0390 (18)0.060 (2)0.054 (2)0.0136 (17)0.0071 (16)0.0197 (17)
C5B0.0356 (18)0.047 (2)0.0394 (16)0.0036 (15)−0.0004 (14)0.0095 (14)
Geometric parameters (Å, º) top
Br—C3A1.900 (3)C1A—H1AA0.9900
N1—C11.389 (4)C1A—H1AB0.9900
N1—C1A1.446 (3)C2A—C7A1.377 (4)
N1—H1A0.8800C2A—C3A1.396 (4)
N2—C1B1.370 (3)C3A—C4A1.380 (4)
N2—C21.423 (3)C4A—C5A1.369 (5)
N2—H2A0.8800C4A—H4AA0.9500
N3—C5B1.336 (4)C5A—C6A1.372 (5)
N3—C1B1.347 (3)C5A—H5AA0.9500
C1—C21.397 (4)C6A—C7A1.398 (4)
C1—C61.401 (4)C6A—H6AA0.9500
C2—C31.384 (4)C7A—H7AA0.9500
C3—C41.383 (4)C1B—C2B1.393 (4)
C3—H3A0.9500C2B—C3B1.359 (4)
C4—C51.372 (4)C2B—H2BA0.9500
C4—H4A0.9500C3B—C4B1.384 (5)
C5—C61.377 (4)C3B—H3BA0.9500
C5—H5A0.9500C4B—C5B1.361 (4)
C6—H6A0.9500C4B—H4BA0.9500
C1A—C2A1.526 (4)C5B—H5BA0.9500
C1—N1—C1A123.2 (2)C7A—C2A—C1A122.8 (3)
C1—N1—H1A118.4C3A—C2A—C1A120.4 (3)
C1A—N1—H1A118.4C4A—C3A—C2A122.6 (3)
C1B—N2—C2124.4 (2)C4A—C3A—Br117.6 (2)
C1B—N2—H2A117.8C2A—C3A—Br119.8 (2)
C2—N2—H2A117.8C5A—C4A—C3A119.1 (3)
C5B—N3—C1B117.5 (2)C5A—C4A—H4AA120.4
N1—C1—C2119.3 (2)C3A—C4A—H4AA120.4
N1—C1—C6122.5 (3)C4A—C5A—C6A120.3 (3)
C2—C1—C6118.1 (3)C4A—C5A—H5AA119.9
C3—C2—C1120.1 (2)C6A—C5A—H5AA119.9
C3—C2—N2121.5 (3)C5A—C6A—C7A120.0 (3)
C1—C2—N2118.4 (3)C5A—C6A—H6AA120.0
C4—C3—C2121.1 (3)C7A—C6A—H6AA120.0
C4—C3—H3A119.5C2A—C7A—C6A121.3 (3)
C2—C3—H3A119.5C2A—C7A—H7AA119.4
C5—C4—C3118.9 (3)C6A—C7A—H7AA119.4
C5—C4—H4A120.5N3—C1B—N2115.0 (2)
C3—C4—H4A120.5N3—C1B—C2B121.4 (3)
C4—C5—C6121.1 (3)N2—C1B—C2B123.7 (3)
C4—C5—H5A119.4C3B—C2B—C1B119.3 (3)
C6—C5—H5A119.4C3B—C2B—H2BA120.4
C5—C6—C1120.6 (3)C1B—C2B—H2BA120.4
C5—C6—H6A119.7C2B—C3B—C4B119.8 (3)
C1—C6—H6A119.7C2B—C3B—H3BA120.1
N1—C1A—C2A115.7 (3)C4B—C3B—H3BA120.1
N1—C1A—H1AA108.4C5B—C4B—C3B117.5 (3)
C2A—C1A—H1AA108.4C5B—C4B—H4BA121.2
N1—C1A—H1AB108.4C3B—C4B—H4BA121.2
C2A—C1A—H1AB108.4N3—C5B—C4B124.5 (3)
H1AA—C1A—H1AB107.4N3—C5B—H5BA117.8
C7A—C2A—C3A116.8 (2)C4B—C5B—H5BA117.8
C1A—N1—C1—C2−162.8 (3)C7A—C2A—C3A—Br179.0 (2)
C1A—N1—C1—C618.9 (4)C1A—C2A—C3A—Br−1.2 (3)
N1—C1—C2—C3179.5 (2)C2A—C3A—C4A—C5A−1.0 (5)
C6—C1—C2—C3−2.0 (4)Br—C3A—C4A—C5A−179.2 (2)
N1—C1—C2—N2−0.4 (4)C3A—C4A—C5A—C6A0.8 (5)
C6—C1—C2—N2178.0 (2)C4A—C5A—C6A—C7A−0.6 (5)
C1B—N2—C2—C3−52.3 (4)C3A—C2A—C7A—C6A−0.6 (4)
C1B—N2—C2—C1127.6 (3)C1A—C2A—C7A—C6A179.6 (3)
C1—C2—C3—C4−0.2 (4)C5A—C6A—C7A—C2A0.4 (5)
N2—C2—C3—C4179.7 (3)C5B—N3—C1B—N2178.6 (2)
C2—C3—C4—C52.1 (4)C5B—N3—C1B—C2B0.2 (4)
C3—C4—C5—C6−1.8 (5)C2—N2—C1B—N3167.2 (2)
C4—C5—C6—C1−0.4 (5)C2—N2—C1B—C2B−14.5 (4)
N1—C1—C6—C5−179.3 (3)N3—C1B—C2B—C3B0.5 (4)
C2—C1—C6—C52.3 (4)N2—C1B—C2B—C3B−177.8 (3)
C1—N1—C1A—C2A68.9 (3)C1B—C2B—C3B—C4B−1.1 (5)
N1—C1A—C2A—C7A−0.8 (4)C2B—C3B—C4B—C5B1.0 (5)
N1—C1A—C2A—C3A179.4 (2)C1B—N3—C5B—C4B−0.3 (4)
C7A—C2A—C3A—C4A0.9 (4)C3B—C4B—C5B—N3−0.3 (5)
C1A—C2A—C3A—C4A−179.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.882.082.952 (3)175
Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formulaC18H16BrN3
Mr354.25
Crystal system, space groupTriclinic, P1
Temperature (K)200
a, b, c (Å)7.9429 (5), 9.5314 (8), 11.0606 (8)
α, β, γ (°)98.741 (6), 90.727 (6), 103.581 (6)
V (Å3)803.48 (10)
Z2
Radiation typeMo Kα
µ (mm−1)2.56
Crystal size (mm)0.51 × 0.43 × 0.16
Data collection
DiffractometerOxford Diffraction Gemini R
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.553, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		8461, 3249, 2038
Rint0.042
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.092, 0.89
No. of reflections3249
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.59, −0.48

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.882.082.952 (3)174.6
Symmetry code: (i) −x+1, −y, −z.
 

Acknowledgements

HSB is grateful to the Department of Science and Technology (DST) for the award of a Ramanna Fellowship. STM thanks the CSIR for a JRF/SRF fellowship. RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

References

First citationAlbéniz, A. C., Espinet, P., Manrique, R. & Pérez-Mateo, A. (2002). Angew. Chem. Int. Ed. 41, 2363–2366.  Google Scholar
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 First citationKuhn, N., Henkel, G. & Kratz, T. (1993). Chem. Ber. 126, 2047–2049.  CrossRef CAS Web of Science Google Scholar
 First citationOxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.  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.

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ISSN: 2056-9890
Volume 65| Part 11| November 2009| Page o2640
https://doi.org/10.1107/S1600536809039130
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