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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3270.
Published online 2009 November 28. doi:  10.1107/S1600536809049575
PMCID: PMC2972169

(4R,5R,10S)-N-(4-Bromo­phen­yl)dehydro­abietamide

Abstract

The title compound, C26H32BrNO, the ring with the amide unit possesses a chair conformation with the two methyl groups in axial positions..

Related literature

For the synthesis and biological activity of dehydro­abietamide derivatives, see: Ntokos et al. (1973 [triangle]); Sepulveda et al. (2005 [triangle]); Fujita et al. (1991 [triangle]). For related structures see: Rao et al. (2006 [triangle], 2007 [triangle]).

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Object name is e-65-o3270-scheme1.jpg

Experimental

Crystal data

  • C26H32BrNO
  • M r = 454.44
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3270-efi1.jpg
  • a = 5.9640 (12) Å
  • b = 11.750 (2) Å
  • c = 32.758 (7) Å
  • V = 2295.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.81 mm−1
  • T = 293 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.714, T max = 0.840
  • 4770 measured reflections
  • 4143 independent reflections
  • 1931 reflections with I > 2σ(I)
  • R int = 0.063
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.133
  • S = 1.00
  • 4143 reflections
  • 257 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.34 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1699 Friedel pairs
  • Flack parameter: −0.003 (16)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo,1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049575/ng2678sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049575/ng2678Isup2.hkl

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

Acknowledgments

The authors thank Professor H. Q. Wang of the Center for Testing and Analysis, Nanjing University, for collecting the X-ray diffraction data.

supplementary crystallographic information

Comment

As a part of our ongoing research on the synthesis and biological activities of dehydroabietic acid derivatives, a serial of dehydroabietamides were synthesized and the crystal structure of the title compound was detected.

Experimental

To a solution of dehydroabietic acid (6.0 g, 0.02 mol) in benzene (40 ml) was added dropwise 2.16 ml of SOCl2 (3.6 g, 0.03 mol), and the mixture was refluxed for 3 h. After cooling to room temperature, the solvent was removed in vacuo, and the residue was then dissolved in 30 ml of benzene, to which triethylamine (2.02 g, 0.02 mol) and p-bromoaniline (3.6 g, 0.021 mol) were added, and the mixture was stirred at room temperature for 24 h. The mixture was then filtered to remove precipitate, the filtrate was evaporated in vacuo to afford a yellowish solid, which was recrystalized in EtOH to give (I) as colorless needles (7.3 g, 81%). Single crystals of (I) suitable for an X-ray diffraction study were obtained by slow evaporation of an acetone solution at room temperature over a period of 5 d.

Refinement

All H atoms were placed geometrically with C—H = 0.93–0.98 Å, N—H = 0.86 Å and included in the refinement in riding motion approximation with Uiso(H) = 1.2Ueq of the carrier atom.

Figures

Fig. 1.
Molecular structure with 30% probability displacement ellipsoids for non-H atoms.

Crystal data

C26H32BrNODx = 1.315 Mg m3
Mr = 454.44Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 25 reflections
a = 5.9640 (12) Åθ = 10–13°
b = 11.750 (2) ŵ = 1.81 mm1
c = 32.758 (7) ÅT = 293 K
V = 2295.6 (8) Å3Block, colourless
Z = 40.20 × 0.10 × 0.10 mm
F(000) = 952

Data collection

Enraf–Nonius CAD-4 diffractometer1931 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
graphiteθmax = 25.3°, θmin = 1.2°
ω/2θ scansh = 0→7
Absorption correction: ψ scan (North et al., 1968)k = 0→14
Tmin = 0.714, Tmax = 0.840l = −39→39
4770 measured reflections3 standard reflections every 200 reflections
4143 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.133w = 1/[σ2(Fo2) + (0.048P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
4143 reflectionsΔρmax = 0.32 e Å3
257 parametersΔρmin = −0.34 e Å3
0 restraintsAbsolute structure: Flack (1983), 1699 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.003 (16)

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*/Ueq
Br0.81958 (18)0.68193 (7)0.09535 (2)0.0947 (4)
N0.8080 (10)1.0580 (5)−0.03060 (15)0.0532 (14)
H0A0.94071.0744−0.03900.064*
O0.4404 (8)1.1045 (4)−0.03859 (15)0.0639 (14)
C1−0.1942 (15)1.1802 (8)−0.2890 (2)0.109
H1A−0.27681.1527−0.31210.164*
H1B−0.19961.2618−0.28850.164*
H1C−0.25921.1506−0.26440.164*
C20.1482 (15)1.1731 (9)−0.3320 (2)0.122 (4)
H2A0.05511.1471−0.35400.183*
H2B0.29291.1377−0.33390.183*
H2C0.16501.2542−0.33370.183*
C30.0417 (14)1.1424 (8)−0.2921 (2)0.094 (3)
H3A0.03891.0591−0.29100.112*
C40.1823 (13)1.1816 (8)−0.2558 (2)0.069 (2)
C50.2310 (12)1.2951 (8)−0.2487 (2)0.067 (2)
H5A0.17771.3507−0.26650.081*
C60.3610 (11)1.3266 (6)−0.21477 (18)0.0565 (18)
H6A0.39511.4029−0.21050.068*
C70.4407 (11)1.2442 (6)−0.18691 (19)0.0487 (18)
C80.3956 (12)1.1298 (6)−0.1947 (2)0.055 (2)
C90.2662 (13)1.1021 (7)−0.2288 (2)0.064 (2)
H9A0.23451.0258−0.23350.077*
C100.5908 (10)1.2836 (5)−0.15146 (18)0.0399 (17)
C110.5900 (9)1.1879 (5)−0.11856 (17)0.0398 (15)
H11A0.43171.1781−0.11140.048*
C120.6589 (13)1.0742 (5)−0.13792 (19)0.0555 (19)
H12A0.79881.0831−0.15270.067*
H12B0.68041.0172−0.11690.067*
C130.4725 (14)1.0366 (6)−0.1672 (2)0.068 (2)
H13A0.52670.9738−0.18370.081*
H13B0.34591.0093−0.15140.081*
C140.4971 (11)1.3919 (5)−0.13126 (18)0.0486 (18)
H14A0.50921.4546−0.15040.058*
H14B0.33931.3806−0.12540.058*
C150.6185 (12)1.4242 (5)−0.09160 (19)0.0575 (19)
H15A0.77391.4421−0.09750.069*
H15B0.54911.4913−0.07990.069*
C160.6080 (11)1.3265 (6)−0.06107 (18)0.0535 (18)
H16A0.45271.3132−0.05370.064*
H16B0.68791.3483−0.03650.064*
C170.7083 (11)1.2159 (5)−0.0775 (2)0.0470 (18)
C180.8244 (11)1.3108 (6)−0.17050 (17)0.0611 (18)
H18A0.80411.3499−0.19600.092*
H18B0.90451.2411−0.17520.092*
H18C0.90831.3580−0.15210.092*
C190.9710 (10)1.2251 (6)−0.0809 (2)0.073 (3)
H19A1.00951.2840−0.09990.110*
H19B1.03101.1538−0.09020.110*
H19C1.03271.2429−0.05460.110*
C200.6416 (14)1.1207 (6)−0.04718 (19)0.0519 (18)
C210.7971 (13)0.9705 (5)−0.00191 (19)0.0477 (17)
C220.9833 (12)0.9004 (5)0.0016 (2)0.0580 (19)
H22A1.10670.9120−0.01530.070*
C230.9861 (13)0.8142 (7)0.0298 (2)0.063 (2)
H23A1.10960.76590.03110.075*
C240.8111 (16)0.7978 (6)0.05601 (19)0.061 (2)
C250.6259 (13)0.8674 (6)0.05292 (19)0.060 (2)
H25A0.50460.85600.07030.072*
C260.6176 (12)0.9541 (6)0.02438 (19)0.058 (2)
H26A0.49241.00100.02280.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.1378 (8)0.0749 (5)0.0715 (5)0.0229 (6)−0.0134 (6)0.0208 (5)
N0.032 (3)0.072 (4)0.055 (3)0.014 (4)0.001 (3)0.012 (3)
O0.032 (3)0.089 (4)0.070 (3)−0.006 (3)0.002 (3)0.028 (3)
C10.1090.1090.1090.0000.0000.000
C20.093 (7)0.220 (11)0.054 (5)0.027 (10)−0.007 (6)−0.031 (7)
C30.084 (7)0.140 (9)0.057 (5)0.005 (6)−0.012 (5)−0.021 (5)
C40.059 (5)0.100 (6)0.048 (4)0.005 (7)0.013 (4)−0.013 (5)
C50.048 (5)0.102 (7)0.051 (4)0.010 (5)−0.004 (4)0.019 (5)
C60.047 (5)0.073 (5)0.049 (4)−0.007 (5)0.005 (4)0.010 (4)
C70.034 (4)0.071 (5)0.041 (4)−0.004 (4)0.008 (4)0.010 (4)
C80.052 (5)0.063 (5)0.050 (4)−0.003 (4)−0.006 (4)−0.009 (4)
C90.062 (6)0.078 (5)0.053 (4)−0.007 (4)0.001 (4)−0.007 (4)
C100.027 (4)0.054 (4)0.039 (4)−0.001 (3)0.004 (3)0.001 (3)
C110.019 (3)0.055 (4)0.045 (3)−0.010 (4)0.000 (3)0.004 (4)
C120.060 (5)0.049 (4)0.058 (4)0.001 (5)0.003 (5)0.012 (3)
C130.092 (6)0.053 (5)0.058 (5)0.009 (5)−0.011 (5)0.005 (4)
C140.046 (4)0.051 (4)0.050 (4)−0.004 (4)0.006 (4)0.007 (3)
C150.066 (5)0.053 (4)0.053 (4)−0.003 (4)−0.003 (5)−0.003 (4)
C160.045 (5)0.064 (4)0.052 (4)−0.008 (4)0.000 (3)−0.007 (4)
C170.027 (4)0.057 (4)0.057 (4)−0.004 (4)0.001 (4)0.012 (3)
C180.042 (4)0.082 (5)0.059 (4)−0.003 (5)0.015 (4)0.021 (4)
C190.028 (4)0.113 (7)0.079 (6)−0.012 (5)−0.011 (4)0.018 (5)
C200.050 (5)0.060 (4)0.046 (4)−0.005 (5)−0.003 (4)−0.004 (3)
C210.047 (4)0.051 (4)0.045 (4)0.011 (4)−0.015 (4)−0.006 (3)
C220.052 (5)0.057 (5)0.066 (5)0.009 (4)−0.010 (4)0.003 (4)
C230.065 (6)0.058 (5)0.064 (5)0.017 (5)−0.015 (4)−0.006 (5)
C240.071 (5)0.058 (5)0.054 (4)0.014 (5)−0.005 (5)−0.009 (4)
C250.068 (6)0.064 (5)0.047 (4)−0.005 (5)0.005 (4)0.005 (4)
C260.051 (5)0.065 (5)0.057 (5)0.013 (4)0.006 (4)0.006 (4)

Geometric parameters (Å, °)

Br—C241.876 (7)C12—C131.534 (9)
N—C201.350 (8)C12—H12A0.9700
N—C211.394 (7)C12—H12B0.9700
N—H0A0.8600C13—H13A0.9700
O—C201.247 (7)C13—H13B0.9700
C1—C31.478 (11)C14—C151.535 (8)
C1—H1A0.9600C14—H14A0.9700
C1—H1B0.9600C14—H14B0.9700
C1—H1C0.9600C15—C161.524 (8)
C2—C31.498 (10)C15—H15A0.9700
C2—H2A0.9600C15—H15B0.9700
C2—H2B0.9600C16—C171.528 (9)
C2—H2C0.9600C16—H16A0.9700
C3—C41.525 (10)C16—H16B0.9700
C3—H3A0.9800C17—C201.548 (8)
C4—C91.382 (10)C17—C191.574 (8)
C4—C51.385 (10)C18—H18A0.9600
C5—C61.406 (9)C18—H18B0.9600
C5—H5A0.9300C18—H18C0.9600
C6—C71.413 (8)C19—H19A0.9600
C6—H6A0.9300C19—H19B0.9600
C7—C81.394 (8)C19—H19C0.9600
C7—C101.538 (9)C21—C221.387 (8)
C8—C91.396 (8)C21—C261.388 (8)
C8—C131.489 (9)C22—C231.372 (9)
C9—H9A0.9300C22—H22A0.9300
C10—C141.540 (8)C23—C241.365 (9)
C10—C111.557 (8)C23—H23A0.9300
C10—C181.559 (8)C24—C251.378 (9)
C11—C121.535 (8)C25—C261.383 (8)
C11—C171.555 (8)C25—H25A0.9300
C11—H11A0.9800C26—H26A0.9300
C20—N—C21129.7 (6)C8—C13—H13B109.0
C20—N—H0A115.1C12—C13—H13B109.0
C21—N—H0A115.1H13A—C13—H13B107.8
C3—C1—H1A109.5C15—C14—C10113.4 (5)
C3—C1—H1B109.5C15—C14—H14A108.9
H1A—C1—H1B109.5C10—C14—H14A108.9
C3—C1—H1C109.5C15—C14—H14B108.9
H1A—C1—H1C109.5C10—C14—H14B108.9
H1B—C1—H1C109.5H14A—C14—H14B107.7
C3—C2—H2A109.5C16—C15—C14110.5 (5)
C3—C2—H2B109.5C16—C15—H15A109.6
H2A—C2—H2B109.5C14—C15—H15A109.6
C3—C2—H2C109.5C16—C15—H15B109.6
H2A—C2—H2C109.5C14—C15—H15B109.6
H2B—C2—H2C109.5H15A—C15—H15B108.1
C1—C3—C2113.0 (8)C15—C16—C17113.1 (5)
C1—C3—C4112.3 (7)C15—C16—H16A108.9
C2—C3—C4112.0 (7)C17—C16—H16A108.9
C1—C3—H3A106.3C15—C16—H16B108.9
C2—C3—H3A106.3C17—C16—H16B108.9
C4—C3—H3A106.3H16A—C16—H16B107.8
C9—C4—C5117.9 (7)C16—C17—C20106.7 (5)
C9—C4—C3119.7 (8)C16—C17—C11107.9 (5)
C5—C4—C3122.5 (8)C20—C17—C11106.6 (5)
C4—C5—C6120.1 (7)C16—C17—C19110.9 (6)
C4—C5—H5A119.9C20—C17—C19110.5 (6)
C6—C5—H5A119.9C11—C17—C19113.9 (5)
C5—C6—C7121.1 (7)C10—C18—H18A109.5
C5—C6—H6A119.4C10—C18—H18B109.5
C7—C6—H6A119.4H18A—C18—H18B109.5
C8—C7—C6118.6 (6)C10—C18—H18C109.5
C8—C7—C10122.7 (6)H18A—C18—H18C109.5
C6—C7—C10118.5 (6)H18B—C18—H18C109.5
C7—C8—C9118.5 (7)C17—C19—H19A109.5
C7—C8—C13122.7 (6)C17—C19—H19B109.5
C9—C8—C13118.8 (7)H19A—C19—H19B109.5
C4—C9—C8123.8 (7)C17—C19—H19C109.5
C4—C9—H9A118.1H19A—C19—H19C109.5
C8—C9—H9A118.1H19B—C19—H19C109.5
C7—C10—C14111.2 (5)O—C20—N122.2 (7)
C7—C10—C11107.7 (5)O—C20—C17120.1 (7)
C14—C10—C11107.3 (5)N—C20—C17117.6 (7)
C7—C10—C18106.3 (5)C22—C21—C26118.9 (6)
C14—C10—C18109.0 (5)C22—C21—N117.1 (7)
C11—C10—C18115.3 (5)C26—C21—N123.9 (7)
C12—C11—C17114.8 (5)C23—C22—C21120.2 (7)
C12—C11—C10110.0 (5)C23—C22—H22A119.9
C17—C11—C10116.4 (5)C21—C22—H22A119.9
C12—C11—H11A104.7C24—C23—C22121.2 (7)
C17—C11—H11A104.7C24—C23—H23A119.4
C10—C11—H11A104.7C22—C23—H23A119.4
C13—C12—C11108.4 (6)C23—C24—C25118.9 (6)
C13—C12—H12A110.0C23—C24—Br120.9 (6)
C11—C12—H12A110.0C25—C24—Br120.2 (6)
C13—C12—H12B110.0C24—C25—C26121.0 (7)
C11—C12—H12B110.0C24—C25—H25A119.5
H12A—C12—H12B108.4C26—C25—H25A119.5
C8—C13—C12112.9 (6)C25—C26—C21119.7 (7)
C8—C13—H13A109.0C25—C26—H26A120.2
C12—C13—H13A109.0C21—C26—H26A120.2
C1—C3—C4—C9113.1 (9)C7—C10—C14—C15170.8 (5)
C2—C3—C4—C9−118.5 (9)C11—C10—C14—C1553.2 (6)
C1—C3—C4—C5−67.0 (11)C18—C10—C14—C15−72.3 (6)
C2—C3—C4—C561.4 (11)C10—C14—C15—C16−57.3 (7)
C9—C4—C5—C6−0.3 (11)C14—C15—C16—C1757.7 (7)
C3—C4—C5—C6179.8 (7)C15—C16—C17—C20−168.5 (6)
C4—C5—C6—C7−1.2 (10)C15—C16—C17—C11−54.3 (7)
C5—C6—C7—C82.6 (10)C15—C16—C17—C1971.0 (7)
C5—C6—C7—C10177.3 (6)C12—C11—C17—C16−175.8 (5)
C6—C7—C8—C9−2.5 (10)C10—C11—C17—C1653.7 (7)
C10—C7—C8—C9−176.9 (6)C12—C11—C17—C20−61.5 (7)
C6—C7—C8—C13179.9 (6)C10—C11—C17—C20168.0 (5)
C10—C7—C8—C135.4 (11)C12—C11—C17—C1960.7 (7)
C5—C4—C9—C80.4 (11)C10—C11—C17—C19−69.9 (7)
C3—C4—C9—C8−179.7 (7)C21—N—C20—O−1.7 (11)
C7—C8—C9—C41.0 (11)C21—N—C20—C17177.8 (6)
C13—C8—C9—C4178.8 (7)C16—C17—C20—O55.3 (8)
C8—C7—C10—C14−141.0 (6)C11—C17—C20—O−59.8 (8)
C6—C7—C10—C1444.5 (7)C19—C17—C20—O176.0 (6)
C8—C7—C10—C11−23.7 (8)C16—C17—C20—N−124.2 (6)
C6—C7—C10—C11161.9 (5)C11—C17—C20—N120.7 (6)
C8—C7—C10—C18100.4 (7)C19—C17—C20—N−3.5 (8)
C6—C7—C10—C18−74.0 (8)C20—N—C21—C22162.9 (6)
C7—C10—C11—C1254.4 (7)C20—N—C21—C26−20.7 (10)
C14—C10—C11—C12174.2 (5)C26—C21—C22—C231.9 (10)
C18—C10—C11—C12−64.0 (7)N—C21—C22—C23178.6 (6)
C7—C10—C11—C17−172.8 (5)C21—C22—C23—C24−2.5 (11)
C14—C10—C11—C17−53.0 (7)C22—C23—C24—C252.1 (11)
C18—C10—C11—C1768.8 (7)C22—C23—C24—Br−178.5 (5)
C17—C11—C12—C13158.1 (5)C23—C24—C25—C26−1.3 (11)
C10—C11—C12—C13−68.2 (6)Br—C24—C25—C26179.3 (5)
C7—C8—C13—C12−17.0 (10)C24—C25—C26—C210.8 (10)
C9—C8—C13—C12165.4 (6)C22—C21—C26—C25−1.1 (10)
C11—C12—C13—C847.0 (7)N—C21—C26—C25−177.5 (6)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2678).

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