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In the title compound, C15H13BrO3, the benzo and quinone rings are planar, while the heterocycle is in a distorted half-chair conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001265/cf6138sup1.cif
Contains datablocks I, bromolapa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001265/cf6138Isup2.hkl
Contains datablock I

CCDC reference: 182625

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.038
  • wR factor = 0.114
  • Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(5) - C(6) = 1.54 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Naphthoquinonic compounds are often found in nature and their biological activity has been associated with various medicinal applications. Their action ranges from antibiotic to antineoplastic activity, although some of them do not presently have a defined function (Pinto et al., 1980). Among the naphthoquinonic compounds, lapachol, lapachones and their derivatives have been of interest to the scientific communities of several countries for more than 100 years because of the large range of biological activities found for these compounds (Subramanian, 1996). Among these activities are: antiviral (Pinto, Pinto et al., 1987), antimalarial (Fieser et al., 1967), antitumor (Li et al., 1999), and activity against trypanosoma cruzi, the protozoan of Chagas disease (Gonçalves et al., 1980; Pinto, Ferreira et al., 1987). As part of a search for compounds with therapeutic activity against a number of parasitic diseases endemic to Brazil, a series of derivatives has been prepared from lapachol (Cruz et al., 1977).

The title compound, (I), is a derivative of lapachol. It was tested in two biological assays, against trypanosoma cruzi (Lopes et al., 1978), and as a protection against the penetration of Schistosomiasis mansoni cercariae in tails of mice (Pinto et al., 1977), and showed, in both tests, discrete biological activity.

The crystal structure of (I) (Fig. 1) shows that the atoms comprising rings A and B and the adjacent C and O atoms are essentially coplanar, with an r.m.s. deviation of 0.039 Å for the 14 atoms. Atoms C2 and C3 are 0.256 (2) and 0.519 (3) Å out of this plane, respectively. Therefore, the C ring assumes a distorted half-chair conformation, the Cremer & Pople (1975) ring-puckering parameters being q2 = 0.407 (2), q3 = 0.314 (2) Å, Q = 0.514 (2) Å, θ = 52.4 (2)° and ϕ = 160.8 (3)°. The overall geometry of both B and C rings is in good agreement with that found for this moiety in a similar compound (Pereira, 1989).

Experimental top

The title compound, (I), was synthesized for the first time by Paternó (1882). However, the method used here was that of Hooker (1892). This substance is easily prepared, in chloroform solvent, by reaction of lapachol with bromine, followed by evaporation and crystallization from ethanol. It was recrystallized from acetone at room temperature.

Refinement top

H atoms were positioned geometrically and refined with a riding model, with isotropic displacement parameters equal to 1.5 (for methyl H atoms) or 1.2Ueq for the parent atom.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom labelling and 50% probability displacement ellipsoids.
(I) top
Crystal data top
C15H13BrO3F(000) = 648
Mr = 321.16Dx = 1.650 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
a = 11.823 (2) ÅCell parameters from 3176 reflections
b = 8.191 (2) Åθ = 1.0–27.5°
c = 13.894 (3) ŵ = 3.18 mm1
β = 106.05 (1)°T = 120 K
V = 1293.1 (5) Å3Prism, orange
Z = 40.22 × 0.15 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
2971 independent reflections
Radiation source: fine-focus sealed tube2601 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 1.8°
ϕ scans, and ω scans with κ offsetsh = 015
Absorption correction: multi-scan
(Blessing, 1995)
k = 010
Tmin = 0.541, Tmax = 0.702l = 1817
5298 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) = 0.114H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.069P)2 + 0.7539P]
where P = (Fo2 + 2Fc2)/3
2971 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 1.05 e Å3
0 restraintsΔρmin = 0.80 e Å3
Crystal data top
C15H13BrO3V = 1293.1 (5) Å3
Mr = 321.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.823 (2) ŵ = 3.18 mm1
b = 8.191 (2) ÅT = 120 K
c = 13.894 (3) Å0.22 × 0.15 × 0.12 mm
β = 106.05 (1)°
Data collection top
Nonius KappaCCD
diffractometer
2971 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
2601 reflections with I > 2σ(I)
Tmin = 0.541, Tmax = 0.702Rint = 0.016
5298 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.09Δρmax = 1.05 e Å3
2971 reflectionsΔρmin = 0.80 e Å3
175 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
Br0.02654 (2)0.10427 (4)0.17914 (2)0.03901 (13)
C100.5407 (2)0.3889 (3)0.10681 (18)0.0239 (5)
H100.48570.47310.10750.029*
C70.7053 (2)0.1448 (3)0.10824 (17)0.0255 (5)
H70.76170.06160.10970.031*
O10.32160 (15)0.31129 (19)0.11720 (13)0.0253 (3)
C6A0.5942 (2)0.1036 (3)0.11613 (17)0.0225 (5)
C4A0.3568 (2)0.0233 (3)0.12886 (17)0.0247 (5)
O30.41395 (17)0.2531 (2)0.14410 (13)0.0316 (4)
O20.63408 (16)0.1795 (2)0.12945 (14)0.0319 (4)
C110.1356 (2)0.2586 (3)0.00585 (19)0.0320 (5)
H11A0.17740.17240.03100.048*
H11B0.13760.35980.04300.048*
H11C0.05360.22550.01490.048*
C30.1879 (2)0.1403 (3)0.17233 (19)0.0273 (5)
H30.23730.16600.24160.033*
C50.4390 (2)0.1098 (3)0.13378 (17)0.0247 (5)
C20.1950 (2)0.2868 (3)0.10532 (18)0.0261 (5)
C40.2359 (2)0.0142 (3)0.13876 (18)0.0272 (5)
H4A0.24040.10210.18860.033*
H4B0.18390.05100.07360.033*
C10A0.5101 (2)0.2262 (3)0.11514 (16)0.0218 (4)
C60.5640 (2)0.0693 (3)0.12655 (17)0.0247 (5)
C10.3918 (2)0.1800 (3)0.12090 (16)0.0229 (4)
C80.7343 (2)0.3067 (3)0.09834 (18)0.0279 (5)
H80.81000.33450.09220.034*
C120.1566 (2)0.4462 (3)0.1419 (2)0.0329 (5)
H12A0.18420.53770.10890.049*
H12C0.19040.45490.21450.049*
H12B0.07060.44910.12590.049*
C90.6517 (2)0.4282 (3)0.09743 (18)0.0269 (5)
H90.67130.53920.09030.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.02618 (18)0.0457 (2)0.0482 (2)0.00395 (10)0.01535 (13)0.00299 (11)
C100.0260 (11)0.0201 (11)0.0240 (11)0.0046 (8)0.0042 (9)0.0000 (8)
C70.0252 (11)0.0262 (11)0.0236 (11)0.0053 (9)0.0046 (9)0.0011 (9)
O10.0233 (8)0.0197 (8)0.0337 (8)0.0046 (6)0.0092 (7)0.0006 (6)
C6A0.0253 (11)0.0218 (11)0.0187 (10)0.0048 (8)0.0031 (8)0.0009 (8)
C4A0.0277 (11)0.0225 (11)0.0234 (10)0.0014 (9)0.0065 (9)0.0001 (8)
O30.0406 (10)0.0203 (8)0.0341 (9)0.0003 (7)0.0106 (8)0.0012 (7)
O20.0319 (9)0.0231 (8)0.0378 (9)0.0088 (7)0.0048 (8)0.0012 (7)
C110.0305 (12)0.0333 (13)0.0301 (12)0.0033 (11)0.0050 (10)0.0014 (10)
C30.0210 (11)0.0330 (12)0.0282 (11)0.0003 (9)0.0074 (9)0.0032 (9)
C50.0325 (13)0.0203 (11)0.0204 (10)0.0018 (9)0.0057 (9)0.0002 (8)
C20.0205 (11)0.0286 (12)0.0293 (11)0.0016 (9)0.0068 (9)0.0022 (9)
C40.0277 (12)0.0255 (11)0.0292 (11)0.0017 (9)0.0089 (9)0.0009 (9)
C10A0.0227 (11)0.0216 (10)0.0203 (10)0.0040 (8)0.0048 (8)0.0006 (8)
C60.0282 (12)0.0221 (10)0.0216 (10)0.0059 (9)0.0030 (9)0.0002 (8)
C10.0262 (11)0.0208 (11)0.0209 (10)0.0042 (9)0.0048 (8)0.0008 (8)
C80.0238 (11)0.0308 (13)0.0292 (11)0.0018 (9)0.0072 (9)0.0006 (9)
C120.0266 (12)0.0318 (13)0.0401 (14)0.0060 (10)0.0090 (10)0.0053 (11)
C90.0284 (12)0.0236 (11)0.0270 (11)0.0008 (9)0.0052 (9)0.0000 (9)
Geometric parameters (Å, º) top
Br—C31.958 (2)C11—H11A0.980
C10—C91.393 (4)C11—H11B0.980
C10—C10A1.394 (3)C11—H11C0.980
C10—H100.950C3—C41.513 (3)
C7—C81.385 (3)C3—C21.536 (4)
C7—C6A1.390 (4)C3—H31.000
C7—H70.950C5—C61.545 (4)
O1—C11.351 (3)C2—C121.515 (3)
O1—C21.473 (3)C4—H4A0.990
C6A—C10A1.411 (3)C4—H4B0.990
C6A—C61.478 (3)C10A—C11.472 (3)
C4A—C11.363 (3)C8—C91.392 (3)
C4A—C51.449 (3)C8—H80.950
C4A—C41.505 (3)C12—H12A0.980
O3—C51.229 (3)C12—H12C0.980
O2—C61.219 (3)C12—H12B0.980
C11—C21.527 (3)C9—H90.950
C9—C10—C10A120.1 (2)O1—C2—C3105.23 (18)
C9—C10—H10119.9C12—C2—C3113.5 (2)
C10A—C10—H10119.9C11—C2—C3114.1 (2)
C8—C7—C6A120.3 (2)C4A—C4—C3107.7 (2)
C8—C7—H7119.8C4A—C4—H4A110.2
C6A—C7—H7119.8C3—C4—H4A110.2
C1—O1—C2119.39 (18)C4A—C4—H4B110.2
C7—C6A—C10A120.4 (2)C3—C4—H4B110.2
C7—C6A—C6120.0 (2)H4A—C4—H4B108.5
C10A—C6A—C6119.6 (2)C10—C10A—C6A118.9 (2)
C1—C4A—C5119.8 (2)C10—C10A—C1121.5 (2)
C1—C4A—C4121.2 (2)C6A—C10A—C1119.6 (2)
C5—C4A—C4118.9 (2)O2—C6—C6A122.2 (2)
C2—C11—H11A109.5O2—C6—C5119.5 (2)
C2—C11—H11B109.5C6A—C6—C5118.3 (2)
H11A—C11—H11B109.5O1—C1—C4A123.8 (2)
C2—C11—H11C109.5O1—C1—C10A112.1 (2)
H11A—C11—H11C109.5C4A—C1—C10A124.2 (2)
H11B—C11—H11C109.5C7—C8—C9119.6 (2)
C4—C3—C2112.2 (2)C7—C8—H8120.2
C4—C3—Br110.05 (17)C9—C8—H8120.2
C2—C3—Br111.39 (16)C2—C12—H12A109.5
C4—C3—H3107.6C2—C12—H12C109.5
C2—C3—H3107.6H12A—C12—H12C109.5
Br—C3—H3107.6C2—C12—H12B109.5
O3—C5—C4A123.0 (2)H12A—C12—H12B109.5
O3—C5—C6118.6 (2)H12C—C12—H12B109.5
C4A—C5—C6118.5 (2)C8—C9—C10120.7 (2)
O1—C2—C12103.55 (19)C8—C9—H9119.6
O1—C2—C11107.63 (19)C10—C9—H9119.6
C12—C2—C11111.9 (2)
C8—C7—C6A—C10A0.6 (4)C7—C6A—C10A—C1178.4 (2)
C8—C7—C6A—C6179.9 (2)C6—C6A—C10A—C12.2 (3)
C1—C4A—C5—O3177.7 (2)C7—C6A—C6—O20.7 (4)
C4—C4A—C5—O31.2 (3)C10A—C6A—C6—O2178.8 (2)
C1—C4A—C5—C61.8 (3)C7—C6A—C6—C5179.3 (2)
C4—C4A—C5—C6178.3 (2)C10A—C6A—C6—C51.3 (3)
C1—O1—C2—C12160.0 (2)O3—C5—C6—O21.3 (3)
C1—O1—C2—C1181.4 (2)C4A—C5—C6—O2179.2 (2)
C1—O1—C2—C340.6 (3)O3—C5—C6—C6A178.8 (2)
C4—C3—C2—O162.8 (2)C4A—C5—C6—C6A0.7 (3)
Br—C3—C2—O1173.26 (14)C2—O1—C1—C4A9.9 (3)
C4—C3—C2—C12175.3 (2)C2—O1—C1—C10A170.00 (18)
Br—C3—C2—C1260.7 (2)C5—C4A—C1—O1179.1 (2)
C4—C3—C2—C1154.9 (3)C4—C4A—C1—O12.7 (3)
Br—C3—C2—C1169.0 (2)C5—C4A—C1—C10A1.0 (3)
C1—C4A—C4—C318.7 (3)C4—C4A—C1—C10A177.4 (2)
C5—C4A—C4—C3157.7 (2)C10—C10A—C1—O10.1 (3)
C2—C3—C4—C4A52.0 (3)C6A—C10A—C1—O1178.84 (19)
Br—C3—C4—C4A176.63 (15)C10—C10A—C1—C4A179.8 (2)
C9—C10—C10A—C6A1.4 (3)C6A—C10A—C1—C4A1.1 (3)
C9—C10—C10A—C1177.4 (2)C6A—C7—C8—C90.7 (4)
C7—C6A—C10A—C100.4 (3)C7—C8—C9—C100.3 (4)
C6—C6A—C10A—C10179.0 (2)C10A—C10—C9—C81.3 (4)

Experimental details

Crystal data
Chemical formulaC15H13BrO3
Mr321.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)11.823 (2), 8.191 (2), 13.894 (3)
β (°) 106.05 (1)
V3)1293.1 (5)
Z4
Radiation typeMo Kα
µ (mm1)3.18
Crystal size (mm)0.22 × 0.15 × 0.12
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.541, 0.702
No. of measured, independent and
observed [I > 2σ(I)] reflections
5298, 2971, 2601
Rint0.016
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.114, 1.09
No. of reflections2971
No. of parameters175
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.05, 0.80

Computer programs: COLLECT (Nonius, 1999), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Br—C31.958 (2)C4A—C41.505 (3)
O1—C11.351 (3)C3—C41.513 (3)
O1—C21.473 (3)C3—C21.536 (4)
C4A—C11.363 (3)
C1—O1—C2119.39 (18)O1—C2—C3105.23 (18)
C4—C3—C2112.2 (2)C4A—C4—C3107.7 (2)
C2—C3—Br111.39 (16)
 

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