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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o469.
Published online 2008 January 18. doi:  10.1107/S1600536808001281
PMCID: PMC2960302

5,11-Dimethyl­dibenzo[b,f][1,5]diazocine-6,12(5H,11H)-dione

Abstract

In the mol­ecule of the title compound, C16H14N2O2, an N,N′-dimethyl­dianthranilide, the two methyl groups are disordered over two positions; site occupation factors were kept fixed as 0.75:0.25 and 0.65:0.35. The dihedral angle between the two benzene rings is 75.57 (3)°.

Related literature

For related literature, see: Nadkarni & Hosangadi (1988 [triangle]). For related structures, see: Ebert et al. (1998 [triangle]); Nonnenmacher et al. (2000 [triangle]); Gordon-Wylie et al. (2004 [triangle]); Olszewska et al. (2004 [triangle]).

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Object name is e-64-0o469-scheme1.jpg

Experimental

Crystal data

  • C16H14N2O2
  • M r = 266.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o469-efi1.jpg
  • a = 11.2715 (10) Å
  • b = 7.9113 (7) Å
  • c = 15.4100 (14) Å
  • β = 101.611 (1)°
  • V = 1346.0 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 150 (2) K
  • 0.55 × 0.42 × 0.24 mm

Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.901, T max = 0.979
  • 12897 measured reflections
  • 3175 independent reflections
  • 2686 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.104
  • S = 1.04
  • 3175 reflections
  • 185 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]) and SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: modiCIFer (Guzei, 2005 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001281/hk2415sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001281/hk2415Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Australian Research Council for a Discovery Project grant to ACT (grant No. DP0345180), and Macquarie University for the award of a Macquarie University Research Development grant to ACT and the award of a PhD scholarship to ABM.

supplementary crystallographic information

Comment

Several structures of the unsubstituted dianthranilide (i.e., lacking methyl groups on the nitrogen atoms) are present in the literature, including ethanol, DMF and pyridine solvates of racemic material (Gordon-Wylie et al., 2004) as well as a DMSO solvate of racemic material, unsolvated racemate and a DMSO solvate of enantiomerically pure crystals (Olszewska et al., 2004).

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges. When the crystal structure was solved, the two methyl groups were found to be disordered. The dihedral angle between the two benzene rings is 75.57 (3)°.

The X-ray crystal structures of three N,N'-disubstituted dianthranilides have also been reported and in all cases they have a smaller dihedral angle between the two aryl rings of the dianthranilide in comparison with the structures of the unsubstituted compounds. The N,N'-di[1-(N-t-butylcarbamoyl)-1-(cyclohexyl)- methyl] (Ebert et al., 1998), N,N'-dibenzyl (Nonnenmacher et al., 2000) and N,N'-dicamphanoyl derivatives (Olszewska et al., 2004) have dihedral angles of 78.2, 83.9 and 77.5°, respectively.

Experimental

The title compound was prepared according to the literature procedure (Nadkarni & Hosangadi, 1988) in 89% yield. Single crystals of (I) were produced from slow evaporation of a dichloromethane solution.

Refinement

When the crystal structure was solved, the two methyl groups were found to be disordered. They were each modelled with disorder over two positions with a common carbon atom. One was assigned a 75:25 split occupancy, the other 65:35. A rotating refinement was used for each methyl position giving staggered orientations for each. H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Synthetic scheme for the synthesis of (I).

Crystal data

C16H14N2O2F000 = 560
Mr = 266.29Dx = 1.314 Mg m3
Monoclinic, P21/cMelting point: 484 K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 11.2715 (10) ÅCell parameters from 5797 reflections
b = 7.9113 (7) Åθ = 2.7–28.3º
c = 15.4100 (14) ŵ = 0.09 mm1
β = 101.611 (1)ºT = 150 (2) K
V = 1346.0 (2) Å3Prism, colourless
Z = 40.55 × 0.42 × 0.24 mm

Data collection

Bruker 1000 CCD area-detector diffractometer3175 independent reflections
Radiation source: fine-focus sealed tube2686 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 150(2) Kθmax = 28.3º
ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −14→14
Tmin = 0.901, Tmax = 0.979k = −10→10
12897 measured reflectionsl = −20→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0528P)2 + 0.3606P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3175 reflectionsΔρmax = 0.23 e Å3
185 parametersΔρmin = −0.23 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/UeqOcc. (<1)
O1−0.03631 (7)0.20770 (12)0.36470 (6)0.0392 (2)
O20.32157 (9)0.56190 (11)0.51403 (6)0.0384 (2)
N10.26191 (9)0.43083 (12)0.38154 (6)0.0293 (2)
N20.11807 (8)0.19261 (12)0.48395 (6)0.0280 (2)
C10.07223 (10)0.19025 (14)0.39558 (8)0.0283 (2)
C20.15986 (10)0.16141 (14)0.33568 (7)0.0270 (2)
C30.14642 (11)0.01939 (15)0.28107 (7)0.0313 (3)
H30.0832−0.05900.28330.038*
C40.22439 (12)−0.00839 (16)0.22364 (8)0.0346 (3)
H40.2150−0.10590.18690.042*
C50.31624 (12)0.10641 (17)0.21977 (7)0.0356 (3)
H50.37060.08640.18110.043*
C60.32876 (11)0.25014 (15)0.27217 (8)0.0323 (3)
H60.39050.32990.26830.039*
C70.25127 (10)0.27809 (14)0.33037 (7)0.0271 (2)
C80.23206 (13)0.59028 (16)0.33401 (9)0.0410 (3)0.75
H8A0.22910.68130.37660.049*0.75
H8B0.15300.58010.29390.049*0.75
H8C0.29410.61620.29960.049*0.75
C8'0.23206 (13)0.59028 (16)0.33401 (9)0.0410 (3)0.25
H8D0.29740.67200.35340.049*0.25
H8E0.15620.63490.34660.049*0.25
H8F0.22260.57070.27020.049*0.25
C90.30500 (10)0.43187 (14)0.47035 (7)0.0271 (2)
C100.33394 (10)0.26308 (13)0.51321 (7)0.0239 (2)
C110.45333 (10)0.22278 (15)0.55095 (7)0.0272 (2)
H110.51660.29940.54600.033*
C120.48022 (10)0.07159 (15)0.59559 (7)0.0304 (3)
H120.56190.04430.62100.036*
C130.38820 (11)−0.04021 (15)0.60338 (7)0.0309 (3)
H130.4071−0.14390.63420.037*
C140.26895 (11)−0.00143 (14)0.56646 (7)0.0291 (2)
H140.2059−0.07770.57230.035*
C150.24198 (9)0.14978 (14)0.52073 (7)0.0243 (2)
C160.03856 (11)0.22890 (17)0.54596 (9)0.0363 (3)0.65
H16A−0.03850.27430.51340.044*0.65
H16B0.07740.31210.58970.044*0.65
H16C0.02360.12460.57630.044*0.65
C16'0.03856 (11)0.22890 (17)0.54596 (9)0.0363 (3)0.35
H16D−0.03480.15960.53090.044*0.35
H16E0.01630.34880.54210.044*0.35
H16F0.08100.20260.60640.044*0.35

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0249 (4)0.0477 (5)0.0415 (5)−0.0008 (4)−0.0015 (3)0.0076 (4)
O20.0516 (6)0.0251 (4)0.0385 (5)−0.0088 (4)0.0088 (4)−0.0029 (3)
N10.0320 (5)0.0229 (5)0.0309 (5)−0.0034 (4)0.0012 (4)0.0057 (4)
N20.0235 (4)0.0306 (5)0.0297 (5)−0.0045 (4)0.0045 (4)0.0013 (4)
C10.0257 (5)0.0237 (5)0.0330 (6)−0.0039 (4)0.0004 (4)0.0043 (4)
C20.0271 (5)0.0272 (5)0.0235 (5)−0.0012 (4)−0.0029 (4)0.0057 (4)
C30.0334 (6)0.0278 (6)0.0283 (5)−0.0026 (4)−0.0045 (4)0.0047 (4)
C40.0440 (7)0.0319 (6)0.0242 (5)0.0037 (5)−0.0023 (5)0.0014 (5)
C50.0417 (7)0.0416 (7)0.0232 (5)0.0062 (5)0.0055 (5)0.0074 (5)
C60.0341 (6)0.0349 (6)0.0267 (5)−0.0022 (5)0.0036 (4)0.0108 (5)
C70.0302 (5)0.0257 (5)0.0226 (5)−0.0011 (4)−0.0014 (4)0.0064 (4)
C80.0490 (8)0.0270 (6)0.0428 (7)−0.0010 (5)−0.0012 (6)0.0110 (5)
C8'0.0490 (8)0.0270 (6)0.0428 (7)−0.0010 (5)−0.0012 (6)0.0110 (5)
C90.0255 (5)0.0248 (5)0.0311 (6)−0.0062 (4)0.0055 (4)0.0019 (4)
C100.0268 (5)0.0245 (5)0.0204 (5)−0.0039 (4)0.0044 (4)−0.0015 (4)
C110.0253 (5)0.0316 (6)0.0245 (5)−0.0051 (4)0.0047 (4)−0.0022 (4)
C120.0277 (5)0.0365 (6)0.0257 (5)0.0022 (4)0.0024 (4)−0.0006 (4)
C130.0392 (6)0.0279 (6)0.0247 (5)0.0016 (5)0.0045 (4)0.0038 (4)
C140.0333 (6)0.0277 (6)0.0258 (5)−0.0071 (4)0.0046 (4)0.0016 (4)
C150.0244 (5)0.0262 (5)0.0217 (5)−0.0042 (4)0.0031 (4)−0.0008 (4)
C160.0297 (6)0.0417 (7)0.0390 (7)−0.0057 (5)0.0107 (5)−0.0040 (5)
C16'0.0297 (6)0.0417 (7)0.0390 (7)−0.0057 (5)0.0107 (5)−0.0040 (5)

Geometric parameters (Å, °)

O1—C11.2280 (13)C6—H60.9500
O2—C91.2229 (14)C8—H8A0.9800
N1—C91.3569 (15)C8—H8B0.9800
N1—C71.4346 (15)C8—H8C0.9800
N1—C81.4635 (14)C9—C101.4964 (15)
N2—C11.3558 (15)C10—C111.3913 (15)
N2—C151.4380 (14)C10—C151.3926 (14)
N2—C161.4642 (15)C11—C121.3827 (16)
C1—C21.4990 (16)C11—H110.9500
C2—C31.3936 (16)C12—C131.3867 (17)
C2—C71.3980 (15)C12—H120.9500
C3—C41.3846 (18)C13—C141.3844 (17)
C3—H30.9500C13—H130.9500
C4—C51.3874 (19)C14—C151.3906 (15)
C4—H40.9500C14—H140.9500
C5—C61.3854 (18)C16—H16A0.9800
C5—H50.9500C16—H16B0.9800
C6—C71.3897 (17)C16—H16C0.9800
C9—N1—C7122.20 (9)N1—C8—H8A109.5
C9—N1—C8119.94 (10)N1—C8—H8B109.5
C7—N1—C8117.74 (9)N1—C8—H8C109.5
C1—N2—C15122.43 (9)O2—C9—N1122.97 (10)
C1—N2—C16119.90 (10)O2—C9—C10120.80 (10)
C15—N2—C16117.55 (9)N1—C9—C10116.21 (9)
O1—C1—N2122.43 (11)C11—C10—C15119.42 (10)
O1—C1—C2120.47 (10)C11—C10—C9119.71 (9)
N2—C1—C2117.09 (9)C15—C10—C9120.75 (10)
C3—C2—C7119.27 (11)C12—C11—C10120.20 (10)
C3—C2—C1119.31 (10)C12—C11—H11119.9
C7—C2—C1121.35 (10)C10—C11—H11119.9
C4—C3—C2120.54 (11)C11—C12—C13120.13 (10)
C4—C3—H3119.7C11—C12—H12119.9
C2—C3—H3119.7C13—C12—H12119.9
C3—C4—C5119.91 (11)C14—C13—C12120.29 (11)
C3—C4—H4120.0C14—C13—H13119.9
C5—C4—H4120.0C12—C13—H13119.9
C6—C5—C4120.11 (12)C13—C14—C15119.60 (10)
C6—C5—H5119.9C13—C14—H14120.2
C4—C5—H5119.9C15—C14—H14120.2
C5—C6—C7120.21 (11)C14—C15—C10120.36 (10)
C5—C6—H6119.9C14—C15—N2119.89 (9)
C7—C6—H6119.9C10—C15—N2119.71 (10)
C6—C7—C2119.94 (11)N2—C16—H16A109.5
C6—C7—N1119.66 (10)N2—C16—H16B109.5
C2—C7—N1120.34 (10)N2—C16—H16C109.5
C15—N2—C1—O1171.43 (10)C7—N1—C9—O2175.40 (11)
C16—N2—C1—O1−4.45 (17)C8—N1—C9—O2−0.55 (18)
C15—N2—C1—C2−7.30 (15)C7—N1—C9—C10−3.60 (15)
C16—N2—C1—C2176.82 (10)C8—N1—C9—C10−179.55 (10)
O1—C1—C2—C3−60.48 (15)O2—C9—C10—C11−64.70 (15)
N2—C1—C2—C3118.28 (11)N1—C9—C10—C11114.32 (11)
O1—C1—C2—C7116.44 (12)O2—C9—C10—C15111.25 (12)
N2—C1—C2—C7−64.81 (14)N1—C9—C10—C15−69.72 (14)
C7—C2—C3—C41.56 (16)C15—C10—C11—C12−0.08 (16)
C1—C2—C3—C4178.54 (10)C9—C10—C11—C12175.93 (10)
C2—C3—C4—C5−0.46 (17)C10—C11—C12—C13−0.36 (16)
C3—C4—C5—C6−1.08 (17)C11—C12—C13—C140.11 (17)
C4—C5—C6—C71.52 (17)C12—C13—C14—C150.59 (17)
C5—C6—C7—C2−0.41 (16)C13—C14—C15—C10−1.03 (16)
C5—C6—C7—N1−177.39 (10)C13—C14—C15—N2−178.59 (10)
C3—C2—C7—C6−1.12 (15)C11—C10—C15—C140.78 (16)
C1—C2—C7—C6−178.04 (10)C9—C10—C15—C14−175.18 (10)
C3—C2—C7—N1175.84 (9)C11—C10—C15—N2178.34 (9)
C1—C2—C7—N1−1.08 (15)C9—C10—C15—N22.37 (15)
C9—N1—C7—C6−109.40 (12)C1—N2—C15—C14−108.33 (12)
C8—N1—C7—C666.63 (14)C16—N2—C15—C1467.64 (14)
C9—N1—C7—C273.63 (14)C1—N2—C15—C1074.10 (14)
C8—N1—C7—C2−110.33 (12)C16—N2—C15—C10−109.93 (12)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2415).

References

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