Literature DB >> 21201776

2,8-Dibromo-4,10-dichloro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazo-cine.

Kai-Xian Zhu, Donald C Craig, Andrew C Try.   

Abstract

The title compound, C(15)H(10)Br(2)Cl(2)N(2), a 2,8-dibromo-4,10-dichloro Tröger's base analogue derived from 4-bromo-2-chloro-aniline, has a dihedral angle of 110.9 (10)° between the two aryl rings, the largest yet measured for a simple dibenzo analogue.

Entities:  

Year:  2008        PMID： 21201776      PMCID： PMC2960512          DOI： 10.1107/S1600536808026226

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For related literature on the synthesis and crystal structures of dihalogenated Tröger’s base analogues, see: Jensen & Wärnmark (2001 ▶); Faroughi et al. (2006a ▶, 2007a ▶,b ▶). For Tröger’s base analogues substituted with multiple electron-withdrawing groups, see: Faroughi et al. (2006b ▶); Bhuiyan et al. (2006 ▶, 2007 ▶); Vande Velde et al. (2008 ▶). For reactions of halogenated Tröger’s base analogues, see: Jensen et al. (2002 ▶); Hof et al. (2005 ▶). For literature on racemization of Tröger’s base analogues and the effect of substituents ortho to the diazo­cine N atoms, see: Lenev et al. (2006 ▶).

Experimental

Crystal data

C15H10Br2Cl2N2 M = 449.0 Orthorhombic, a = 7.910 (2) Å b = 12.601 (3) Å c = 15.230 (4) Å V = 1518.0 (7) Å3 Z = 4 Mo Kα radiation μ = 5.64 mm−1 T = 294 K 0.30 × 0.12 × 0.07 mm

Data collection

Enraf–Nonius CAD-4 diffractometer Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T min = 0.52, T max = 0.69 1394 measured reflections 1394 independent reflections 1028 reflections with I > 2σ(I) 1 standard reflection frequency: 30 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.056 wR(F 2) = 0.061 S = 1.61 1394 reflections 189 parameters H-atom parameters constrained Δρmax = 0.98 e Å−3 Δρmin = −1.02 e Å−3 Absolute structure: Flack (1983 ▶) Flack parameter: 0.09 (2) Data collection: CAD-4 (Schagen et al., 1989 ▶); cell refinement: CAD-4; data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: RAELS (Rae, 1996 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: local programs. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026226/tk2290sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026226/tk2290Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C15H10Br2Cl2N2Dx = 1.96 Mg m−3
Mr = 449.0Melting point: 471 K
Orthorhombic, Pca21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 11 reflections
a = 7.910 (2) Åθ = 10–11º
b = 12.601 (3) ŵ = 5.64 mm−1
c = 15.230 (4) ÅT = 294 K
V = 1518.0 (7) Å3Prism, colourless
Z = 40.30 × 0.12 × 0.07 mm
F000 = 872.0
Enraf–Nonius CAD-4 diffractometerθmax = 25º
ω–2θ scansh = 0→9
Absorption correction: analyticalde Meulenaer & Tompa (1965)k = 0→14
Tmin = 0.52, Tmax = 0.69l = −18→0
1394 measured reflections1 standard reflections
1394 independent reflections every 30 min
1028 reflections with I > 2σ(I) intensity decay: none
Refinement on F  w = 1/[σ2(F) + 0.0004F2]
R[F2 > 2σ(F2)] = 0.056(Δ/σ)max = 0.002
wR(F2) = 0.061Δρmax = 0.98 e Å−3
S = 1.61Δρmin = −1.02 e Å−3
1394 reflectionsExtinction correction: none
189 parametersAbsolute structure: Flack (1983), 0 Friedel pairs
H-atom parameters constrainedFlack parameter: 0.09 (2)
xyzUiso*/Ueq
Br10.8061 (2)0.6867 (1)0.3991 (1)0.0585 (5)
Br20.2324 (2)0.0800 (1)0.0428 (2)0.0527 (5)
Cl10.9770 (5)0.5167 (4)0.0779 (3)0.057 (1)
Cl20.5654 (5)0.0565 (3)0.3603 (3)0.052 (1)
N10.9460 (14)0.3064 (10)0.1658 (8)0.041 (3)
N20.8319 (15)0.1842 (9)0.2739 (8)0.044 (3)
C10.9798 (19)0.2123 (12)0.2198 (10)0.044 (4)
C20.8998 (18)0.3929 (12)0.2193 (10)0.043 (4)
C30.8445 (18)0.3790 (11)0.3054 (8)0.041 (4)
C40.817 (2)0.2693 (12)0.3414 (8)0.049 (4)
C50.6842 (19)0.1696 (11)0.2226 (9)0.039 (4)
C60.6740 (19)0.2086 (11)0.1360 (9)0.036 (4)
C70.8206 (17)0.2753 (12)0.0978 (9)0.040 (4)
C80.9155 (17)0.4984 (13)0.1855 (9)0.043 (4)
C90.8825 (19)0.5861 (12)0.2397 (11)0.048 (4)
C100.839 (2)0.5684 (13)0.3247 (11)0.050 (4)
C110.818 (2)0.4666 (13)0.3570 (10)0.056 (4)
C120.5565 (17)0.1082 (10)0.2538 (8)0.031 (3)
C130.4158 (17)0.0854 (10)0.2036 (8)0.035 (3)
C140.4117 (17)0.1221 (11)0.1168 (9)0.040 (4)
C150.5433 (19)0.1819 (10)0.0853 (9)0.034 (3)
H1C11.07800.22730.25930.044
H2C11.00780.15130.18040.044
H1C40.70080.26600.36740.049
H2C40.90270.25590.38830.049
H1C70.77260.34100.07080.040
H2C70.87940.23260.05170.040
HC90.89060.66000.21620.048
HC110.78250.45670.41950.056
HC130.31940.04380.22860.035
HC150.54110.20610.02280.034
U11U22U33U12U13U23
Br10.060 (1)0.060 (1)0.0549 (9)−0.0011 (8)−0.001 (1)−0.0138 (9)
Br20.0470 (9)0.0650 (9)0.0461 (8)−0.0118 (8)−0.0026 (9)−0.0091 (9)
Cl10.061 (3)0.066 (3)0.044 (2)−0.019 (2)0.010 (2)0.000 (2)
Cl20.063 (3)0.056 (2)0.037 (2)0.000 (2)0.006 (2)0.018 (2)
N10.029 (7)0.058 (8)0.037 (7)0.001 (6)0.002 (6)−0.003 (6)
N20.046 (7)0.048 (7)0.038 (7)0.004 (6)−0.009 (6)0.020 (6)
C10.029 (9)0.067 (9)0.036 (8)0.005 (8)−0.016 (7)0.012 (8)
C20.051 (9)0.043 (9)0.034 (8)0.009 (8)0.020 (8)−0.006 (7)
C30.045 (9)0.059 (9)0.019 (8)−0.012 (8)−0.004 (7)−0.005 (7)
C40.083 (9)0.053 (8)0.013 (7)0.004 (9)−0.006 (7)0.007 (7)
C50.048 (9)0.043 (9)0.026 (7)0.000 (7)0.013 (7)0.007 (7)
C60.039 (8)0.042 (8)0.026 (8)0.010 (8)0.002 (6)−0.006 (7)
C70.037 (8)0.052 (9)0.030 (8)−0.007 (8)0.007 (7)−0.002 (7)
C80.029 (8)0.062 (9)0.039 (9)−0.002 (8)−0.002 (7)0.004 (9)
C90.047 (9)0.038 (9)0.059 (9)−0.010 (8)−0.001 (8)−0.007 (8)
C100.047 (9)0.057 (9)0.046 (9)−0.005 (8)0.017 (8)−0.007 (8)
C110.085 (9)0.052 (9)0.029 (8)−0.011 (9)0.009 (9)−0.007 (8)
C120.037 (8)0.032 (8)0.024 (7)0.009 (7)0.010 (6)−0.002 (6)
C130.046 (9)0.043 (9)0.016 (6)0.014 (8)0.001 (6)0.000 (7)
C140.029 (8)0.039 (8)0.052 (9)0.006 (7)0.010 (7)−0.015 (8)
C150.034 (8)0.039 (8)0.027 (7)0.004 (7)0.009 (7)−0.004 (7)
Br1—C101.890 (15)C4—H2C41.000
Br2—C141.888 (14)C5—C61.410 (18)
Cl1—C81.724 (14)C5—C121.358 (18)
Cl2—C121.750 (13)C6—C71.546 (20)
N1—C11.468 (18)C6—C151.333 (19)
N1—C21.409 (17)C7—H1C71.000
N1—C71.487 (18)C7—H2C71.000
N2—C11.474 (19)C8—C91.404 (20)
N2—C41.491 (18)C9—C101.357 (19)
N2—C51.417 (18)C9—HC91.000
C1—H1C11.000C10—C111.385 (21)
C1—H2C11.000C11—HC111.000
C2—C31.394 (18)C12—C131.381 (17)
C2—C81.431 (20)C13—C141.402 (18)
C3—C41.503 (20)C13—HC131.000
C3—C111.371 (20)C14—C151.371 (19)
C4—H1C41.000C15—HC151.000
C1—N1—C2110.4 (12)N1—C7—C6112.5 (11)
C1—N1—C7107.4 (11)N1—C7—H1C7108.7
C2—N1—C7115.7 (11)N1—C7—H2C7108.7
C1—N2—C4106.0 (11)C6—C7—H1C7108.7
C1—N2—C5112.2 (11)C6—C7—H2C7108.7
C4—N2—C5114.1 (12)H1C7—C7—H2C7109.5
N1—C1—N2111.3 (11)Cl1—C8—C2119.3 (11)
N1—C1—H1C1109.0Cl1—C8—C9120.4 (12)
N1—C1—H2C1109.0C2—C8—C9120.2 (12)
N2—C1—H1C1109.0C8—C9—C10118.6 (15)
N2—C1—H2C1109.0C8—C9—HC9120.7
H1C1—C1—H2C1109.5C10—C9—HC9120.7
N1—C2—C3121.9 (14)Br1—C10—C9118.5 (13)
N1—C2—C8119.2 (12)Br1—C10—C11120.0 (11)
C3—C2—C8118.8 (13)C9—C10—C11121.4 (15)
C2—C3—C4120.3 (13)C3—C11—C10121.6 (14)
C2—C3—C11119.1 (14)C3—C11—HC11119.2
C4—C3—C11120.6 (12)C10—C11—HC11119.2
N2—C4—C3113.5 (10)Cl2—C12—C5120.5 (12)
N2—C4—H1C4108.4Cl2—C12—C13117.9 (10)
N2—C4—H2C4108.4C5—C12—C13121.6 (13)
C3—C4—H1C4108.4C12—C13—C14118.2 (13)
C3—C4—H2C4108.4C12—C13—HC13120.9
H1C4—C4—H2C4109.5C14—C13—HC13120.9
N2—C5—C6121.2 (13)Br2—C14—C13119.2 (11)
N2—C5—C12119.6 (13)Br2—C14—C15121.0 (11)
C6—C5—C12118.9 (15)C13—C14—C15119.6 (13)
C5—C6—C7119.8 (13)C6—C15—C14121.6 (13)
C5—C6—C15119.9 (14)C6—C15—HC15119.2
C7—C6—C15120.1 (12)C14—C15—HC15119.2
C2—N1—C1—N257.5 (15)C2—C3—C11—C102.3 (24)
C2—N1—C1—H1C1−62.8C2—C3—C11—HC11−177.7
C2—N1—C1—H2C1177.8C4—C3—C11—C10−178.6 (16)
C7—N1—C1—N2−69.4 (15)C4—C3—C11—HC111.4
C7—N1—C1—H1C1170.3N2—C5—C6—C7−4.4 (20)
C7—N1—C1—H2C150.8N2—C5—C6—C15171.2 (13)
C1—N1—C2—C3−18.2 (18)C12—C5—C6—C7−177.9 (12)
C1—N1—C2—C8159.5 (13)C12—C5—C6—C15−2.3 (20)
C7—N1—C2—C3103.9 (16)N2—C5—C12—Cl25.4 (18)
C7—N1—C2—C8−78.3 (17)N2—C5—C12—C13−175.2 (12)
C1—N1—C7—C644.6 (15)C6—C5—C12—Cl2179.1 (10)
C1—N1—C7—H1C7165.1C6—C5—C12—C13−1.6 (20)
C1—N1—C7—H2C7−75.8C5—C6—C7—N1−10.2 (17)
C2—N1—C7—C6−79.1 (15)C5—C6—C7—H1C7−130.7
C2—N1—C7—H1C741.3C5—C6—C7—H2C7110.2
C2—N1—C7—H2C7160.4C15—C6—C7—N1174.2 (13)
C4—N2—C1—N1−69.8 (13)C15—C6—C7—H1C753.8
C4—N2—C1—H1C150.5C15—C6—C7—H2C7−65.3
C4—N2—C1—H2C1169.9C5—C6—C15—C143.9 (21)
C5—N2—C1—N155.3 (16)C5—C6—C15—HC15−176.1
C5—N2—C1—H1C1175.6C7—C6—C15—C14179.5 (12)
C5—N2—C1—H2C1−65.0C7—C6—C15—HC15−0.5
C1—N2—C4—C342.4 (15)Cl1—C8—C9—C10−178.1 (12)
C1—N2—C4—H1C4163.0Cl1—C8—C9—HC91.9
C1—N2—C4—H2C4−78.2C2—C8—C9—C101.4 (23)
C5—N2—C4—C3−81.5 (16)C2—C8—C9—HC9−178.6
C5—N2—C4—H1C439.1C8—C9—C10—Br1176.8 (11)
C5—N2—C4—H2C4157.9C8—C9—C10—C11−3.7 (25)
C1—N2—C5—C6−17.3 (19)HC9—C9—C10—Br1−3.2
C1—N2—C5—C12156.2 (13)HC9—C9—C10—C11176.3
C4—N2—C5—C6103.2 (14)Br1—C10—C11—C3−178.6 (12)
C4—N2—C5—C12−83.3 (16)Br1—C10—C11—HC111.4
N1—C2—C3—C4−5.9 (21)C9—C10—C11—C31.9 (26)
N1—C2—C3—C11173.3 (14)C9—C10—C11—HC11−178.1
C8—C2—C3—C4176.4 (14)Cl2—C12—C13—C14−176.9 (10)
C8—C2—C3—C11−4.4 (21)Cl2—C12—C13—HC133.1
N1—C2—C8—Cl14.3 (19)C5—C12—C13—C143.7 (19)
N1—C2—C8—C9−175.2 (13)C5—C12—C13—HC13−176.3
C3—C2—C8—Cl1−177.9 (11)C12—C13—C14—Br2173.5 (9)
C3—C2—C8—C92.6 (21)C12—C13—C14—C15−2.1 (18)
C2—C3—C4—N2−7.5 (20)HC13—C13—C14—Br2−6.5
C2—C3—C4—H1C4−128.1HC13—C13—C14—C15177.9
C2—C3—C4—H2C4113.1Br2—C14—C15—C6−177.3 (11)
C11—C3—C4—N2173.3 (14)Br2—C14—C15—HC152.7
C11—C3—C4—H1C452.7C13—C14—C15—C6−1.7 (20)
C11—C3—C4—H2C4−66.1C13—C14—C15—HC15178.3
  2 in total

1.  Bis-ortho-substitution by methyl groups dramatically increases the racemization barrier of Tröger bases.

Authors:  Denis A Lenev; Konstantin A Lyssenko; Denis G Golovanov; Volker Buss; Remir G Kostyanovsky
Journal:  Chemistry       Date:  2006-08-16       Impact factor: 5.236

2.  Racemic 1,2,3,4,7,8,9,10-octa-fluoro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazo-cine: an octa-fluorinated analogue of Tröger's base.

Authors:  Christophe M L Vande Velde; Delphine Didier; Frank Blockhuys; Sergey Sergeyev
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-01-30
  2 in total
  1 in total

1.  Diethyl 6H,12H-5,11-methano-dibenzo[b,f][1,5]diazo-cine-1,7-dicarboxyl-ate.

Authors:  M Delower H Bhuiyan; Jack K Clegg; Andrew C Try
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-12-20
  1 in total

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