3-(2,4-Dibromo­anilino)-2,2-dimethyl-2,3-dihydro­naphtho[1,2-b]furan-4,5-dione: a new substituted aryl­amino nor-β-lapachone derivative

Silva, E.N. da Jr; De Simone, C.A.; Goulart, M.O.F.; Andrade, C.K.Z.; Silva, R.S.F.; Pinto, A.V.

doi:10.1107/S1600536808034545

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2348

doi:10.1107/S1600536808034545

Open

access

3-(2,4-Dibromoanilino)-2,2-dimethyl-2,3-dihydronaphtho[1,2-b]furan-4,5-dione: a new substituted arylamino nor-β-lapachone derivative

Eufrânio N. da Silva Jr,^a Carlos A. De Simone,^b ^* Marília O. F. Goulart,^b Carlos K. Z. Andrade,^a Raphael S. F. Silva ^c and Antonio V. Pinto ^c

^aInstituto de Química, Universidade de Brasília, 70910-970 Brasília, DF, Brazil, ^bInstituto de Química e Biotecnologia, Universidade Federal de Alagoas, 57072-970 Maceió, AL, Brazil, and ^cNućleo de Pesquisas em Produtos Naturais, Universidade Federal do Rio de Janeiro, 21944-971 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cas@qui.ufal.br

(Received 22 September 2008; accepted 22 October 2008; online 13 November 2008)

The title compound, C₂₀H₁₅Br₂NO₃, shows the furan ring to adopt a half-chair conformation and the two ring systems to be approximately perpendicular [dihedral angle = 71.0 (2)°]. In the crystal structure, intermolecular C—H⋯O contacts link the molecules.

Related literature

For general background, see: Hillard et al. (2008 ); Pinto et al., (1997 ); Dos Santos et al. (2001 ); Lima et al. (2004 ). For related structures and biological activity, see: da Silva Júnior et al. (2007 , 2008 ); Lima et al. (2002 ). For the synthesis, see: da Silva Júnior et al. (2007, 2008). For geometric analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₀H₁₅Br₂NO₃
M_r = 477.15
Triclinic, $[P \overline 1]$
a = 8.1430 (3) Å
b = 11.2584 (4) Å
c = 11.4742 (5) Å
α = 112.073 (2)°
β = 95.546 (2)°
γ = 108.696 (2)°
V = 894.70 (6) Å³
Z = 2
Mo Kα radiation
μ = 4.55 mm⁻¹
T = 293 (2) K
0.31 × 0.28 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.272, T_max = 0.490
9784 measured reflections
4099 independent reflections
3610 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.139
S = 1.09
4070 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −1.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.98	2.64	3.347 (6)	129
C1′′—H1A⋯O2ⁱ	0.96	2.67	3.389 (6)	132
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034545/tk2311sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034545/tk2311Isup2.hkl

checkCIF report

Comment top

The search for substances with pharmacological activity has grown exponentially in recent years and quinones play a major role as bioreductive drugs, reactive oxygen species (ROS) enhancers, and redox catalysts (Hillard et al., 2008). Substances such as lapachol (I), (Pinto et al., 1997; dos Santos et al., 2001; Lima et al., 2004), β-lapachone (II) (Hillard et al., 2008) and nor-β-lapachone (III) (da Silva Júnior et al., 2007), Scheme 1, are prototypes that can be used as starting points for the synthesis of new bioactive molecules. In this context, different compounds with anti-cancer activity (da Silva Júnior et al., 2007), trypanocides (da Silva Júnior et al., 2008), molluscicides (Lima et al., 2002) among others, were synthesized. The introduction of arylamino groups in the furan ring of III retained/enhanced the anticancer activity against six cancer cell lines with IC₅₀ values below 1µg/ml (da Silva Júnior et al., 2007), as well as intensified trypanocidal activity (da Silva Júnior et al., 2008), demonstrating clearly that the arylamino group is important for pharmacological activity. In this paper, we report the molecular and crystal structure of (IV) that was easily obtained as described in the literature (da Silva Júnior et al., 2007; 2008).

The atoms of the naphthoquinonic ring of (IV), Fig. 1, are co-planar and the greatest deviation from their least-squares plane is exhibited by atom C5 [0.069 (4) Å]. The O1 atom lies in the mean least-square plane of the naphthoquinonic ring with a deviation of 0.051 (3) Å while atoms O2 and O3 are -0.129 (3) and 0.212 (4)Å out of that plane, respectively. The furane ring adopts a half chair conformation and the calculated puckering parameters are: q₂ = 0.229 (4) Å and ϕ = -12 8.04 (1)° (Cremer & Pople, 1975). The dihedral angle between planes passing through atoms C1'-C6' of the aromatic ring and the naphthoquinonic ring is 71.0 (2) °. In the crystal packing, molecules interact through two intermolecular C—H···O contacts, Table 1.

Related literature top

For general background, see: Hillard et al. (2008); Pinto et al., (1997); Dos Santos et al. (2001); Lima et al. (2004). For related structures and biological activity, see: da Silva Júnior et al. (2007, 2008); Lima et al. (2002). For the synthesis, see: da Silva Júnior et al., (2007, 2008). For geometric analysis, see: Cremer & Pople (1975).

Experimental top

To a chloroform (25mL) solution of the nor-lapachol (2-hydroxy-3-(2-methylprop-1-enyl)naphthalene-1,4-dione, 228 mg, 1 mmol), bromine (2 mL, 38 mmol) was added. The bromo intermediate, 3-bromo-2,2-dimethyl-2,3-dihydro-naphtho[1,2-b]furan-4,5-dione, precipitated immediately as an orange solid. Over this mixture, an excess of 2,4-dibromobenzenamine was added and the mixture was left under agitation overnight. After the addition of water (50 ml), the organic phase was separated and washed with 10% HCl (3 x 50 ml), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The arylaminoderivative,3-(2',4'-dibromophenylamine)-2H,3H-2,2- dimethylnaphtho[1,2 - b]furan-4,5-dione species, was purified by column chromatography over silica-gel, using as eluent a gradient mixture of hexane/ethyl acetate (9/1 to 7/3) with increasing polarity and obtained as a red solid (330 mg, 0.70 mmol, 70% yield). ¹H NMR (300 MHz, CDCl₃) δ: 8.14 (1H, dd, J = 6.7, 1.3 Hz), 7.76–7.63 (3H, m), 7.56 (1H, d, J = 2.0 Hz), 7.30 (1H, dd, J = 8.8, 2.0 Hz), 6.53 (1H, d, J = 8.8 Hz), 4.83 (1H, d, J = 7.5 Hz), 4.48 (NH, d,J = 7.5 Hz), 1.66 (3H, s), 1.54 (3H, s). ¹³C NMR (75 MHz, CDCl₃) δ: 180.6 (C=O), 175.0 (C=O), 169.7 (C_q), 143.0 (C_q), 134.6 (CH), 132.6 (CH),131.1 (CH), 131.0 (C_q), 129.5 (CH), 127.1 (C_q), 125.1 (CH), 114.4 (C_q),112.6(CH), 110.2 (C_q), 108.9 (C_q), 96.0 (C_q), 134.5(CH), 61.2 (CH), 27.5 (CH₃), 21.6 (CH₃).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Projection of a molecule of (IV), showing the atom labelling with 50% probability displacement ellipsoids.

3-(2,4-Dibromoanilino)-2,2-dimethyl-2,3-dihydronaphtho[1,2-b]furan- 4,5-dione top

Crystal data top

C₂₀H₁₅Br₂NO₃	Z = 2
M_r = 477.15	F(000) = 472
Triclinic, P1	D_x = 1.771 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1430 (3) Å	Cell parameters from 7882 reflections
b = 11.2584 (4) Å	θ = 1.0–27.5°
c = 11.4742 (5) Å	µ = 4.55 mm⁻¹
α = 112.073 (2)°	T = 293 K
β = 95.546 (2)°	Plate, colorless
γ = 108.696 (2)°	0.31 × 0.28 × 0.16 mm
V = 894.70 (6) Å³

Data collection top

Nonius KappaCCD diffractometer	4099 independent reflections
Radiation source: Enraf Nonius FR590	3610 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.032
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
CCD rotation images, thick slices scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.272, T_max = 0.490	l = −14→14
9784 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0642P)² + 1.7472P] where P = (F_o² + 2F_c²)/3
4070 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −1.49 e Å⁻³

Crystal data top

C₂₀H₁₅Br₂NO₃	γ = 108.696 (2)°
M_r = 477.15	V = 894.70 (6) Å³
Triclinic, P1	Z = 2
a = 8.1430 (3) Å	Mo Kα radiation
b = 11.2584 (4) Å	µ = 4.55 mm⁻¹
c = 11.4742 (5) Å	T = 293 K
α = 112.073 (2)°	0.31 × 0.28 × 0.16 mm
β = 95.546 (2)°

Data collection top

Nonius KappaCCD diffractometer	4099 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3610 reflections with I > 2σ(I)
T_min = 0.272, T_max = 0.490	R_int = 0.032
9784 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.09	Δρ_max = 0.59 e Å⁻³
4070 reflections	Δρ_min = −1.49 e Å⁻³
235 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

	x	y	z	U_iso*/U_eq
Br1	0.13493 (6)	0.15969 (6)	0.15092 (5)	0.06302 (18)
Br2	0.61904 (6)	0.13670 (4)	−0.16856 (4)	0.04728 (15)
O1	0.5871 (4)	0.4358 (3)	0.6646 (3)	0.0405 (6)
O2	0.2827 (4)	−0.0404 (3)	0.4343 (3)	0.0475 (7)
O3	0.0912 (5)	−0.0405 (3)	0.6162 (4)	0.0647 (10)
N1	0.4572 (4)	0.2348 (4)	0.3578 (3)	0.0388 (7)
H1	0.3585	0.2460	0.3654	0.047*
C2	0.6940 (5)	0.3902 (4)	0.5704 (4)	0.0376 (8)
C3	0.5652 (5)	0.2412 (4)	0.4710 (4)	0.0343 (7)
H3	0.6291	0.1787	0.4452	0.041*
C3A	0.4399 (5)	0.2026 (4)	0.5504 (3)	0.0335 (7)
C4	0.3082 (5)	0.0695 (4)	0.5251 (4)	0.0355 (7)
C5	0.1911 (5)	0.0697 (4)	0.6241 (4)	0.0396 (8)
C5A	0.2076 (5)	0.2057 (4)	0.7271 (4)	0.0356 (7)
C6	0.0916 (5)	0.2100 (4)	0.8081 (4)	0.0430 (9)
H6	0.0005	0.1284	0.7967	0.052*
C7	0.1114 (6)	0.3356 (5)	0.9059 (4)	0.0487 (10)
H7	0.0348	0.3379	0.9610	0.058*
C8	0.2437 (7)	0.4573 (5)	0.9222 (5)	0.0503 (10)
H8	0.2560	0.5413	0.9882	0.060*
C9	0.3589 (6)	0.4550 (4)	0.8403 (4)	0.0449 (9)
H9	0.4480	0.5374	0.8514	0.054*
C9A	0.3410 (5)	0.3304 (4)	0.7427 (4)	0.0347 (7)
C9B	0.4547 (5)	0.3204 (4)	0.6524 (4)	0.0339 (7)
C1'	0.4990 (5)	0.2127 (4)	0.2403 (4)	0.0336 (7)
C2'	0.3688 (5)	0.1795 (4)	0.1324 (4)	0.0349 (7)
C3'	0.4010 (5)	0.1562 (4)	0.0115 (4)	0.0384 (8)
H3'	0.3101	0.1327	−0.0586	0.046*
C4'	0.5725 (5)	0.1686 (4)	−0.0031 (4)	0.0370 (8)
C5'	0.7048 (6)	0.2006 (5)	0.1004 (4)	0.0428 (9)
H5'	0.8189	0.2081	0.0898	0.051*
C6'	0.6691 (5)	0.2220 (4)	0.2212 (4)	0.0406 (8)
H6'	0.7597	0.2429	0.2904	0.049*
C1''	0.8530 (6)	0.3854 (5)	0.6478 (5)	0.0509 (10)
H1A	0.8108	0.3159	0.6791	0.076*
H1B	0.9175	0.4744	0.7201	0.076*
H1C	0.9308	0.3628	0.5930	0.076*
C2''	0.7497 (6)	0.4983 (4)	0.5182 (5)	0.0466 (9)
H2A	0.6454	0.4971	0.4703	0.070*
H2B	0.8268	0.4777	0.4621	0.070*
H2C	0.8124	0.5886	0.5891	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0428 (3)	0.0937 (4)	0.0536 (3)	0.0282 (3)	0.0146 (2)	0.0306 (3)
Br2	0.0576 (3)	0.0534 (3)	0.0380 (2)	0.0228 (2)	0.02256 (19)	0.02340 (19)
O1	0.0463 (15)	0.0328 (12)	0.0396 (14)	0.0101 (11)	0.0189 (12)	0.0153 (11)
O2	0.0541 (17)	0.0357 (14)	0.0432 (16)	0.0129 (12)	0.0138 (13)	0.0105 (12)
O3	0.075 (2)	0.0385 (16)	0.074 (2)	0.0084 (15)	0.0367 (19)	0.0246 (16)
N1	0.0419 (17)	0.0533 (19)	0.0326 (16)	0.0262 (15)	0.0153 (13)	0.0222 (14)
C2	0.0393 (19)	0.0401 (19)	0.0381 (19)	0.0139 (15)	0.0151 (16)	0.0217 (16)
C3	0.0386 (18)	0.0405 (18)	0.0338 (18)	0.0199 (15)	0.0151 (15)	0.0209 (15)
C3A	0.0394 (18)	0.0368 (17)	0.0285 (16)	0.0143 (15)	0.0105 (14)	0.0184 (14)
C4	0.0398 (19)	0.0353 (17)	0.0323 (18)	0.0144 (15)	0.0083 (14)	0.0157 (14)
C5	0.0404 (19)	0.0386 (19)	0.041 (2)	0.0121 (15)	0.0120 (16)	0.0207 (16)
C5A	0.0364 (18)	0.0389 (18)	0.0357 (18)	0.0140 (15)	0.0106 (15)	0.0204 (15)
C6	0.0378 (19)	0.050 (2)	0.048 (2)	0.0166 (17)	0.0189 (17)	0.0268 (18)
C7	0.051 (2)	0.062 (3)	0.045 (2)	0.028 (2)	0.0240 (19)	0.027 (2)
C8	0.061 (3)	0.049 (2)	0.042 (2)	0.025 (2)	0.022 (2)	0.0159 (18)
C9	0.054 (2)	0.0382 (19)	0.041 (2)	0.0149 (17)	0.0172 (18)	0.0162 (17)
C9A	0.0393 (18)	0.0355 (17)	0.0302 (17)	0.0124 (14)	0.0101 (14)	0.0165 (14)
C9B	0.0392 (18)	0.0356 (17)	0.0329 (17)	0.0141 (14)	0.0123 (14)	0.0203 (14)
C1'	0.0389 (18)	0.0373 (17)	0.0314 (17)	0.0177 (15)	0.0121 (14)	0.0185 (14)
C2'	0.0329 (17)	0.0388 (18)	0.0382 (19)	0.0162 (14)	0.0122 (14)	0.0192 (15)
C3'	0.043 (2)	0.043 (2)	0.0331 (18)	0.0185 (16)	0.0097 (15)	0.0195 (16)
C4'	0.046 (2)	0.0383 (18)	0.0341 (18)	0.0186 (16)	0.0189 (16)	0.0199 (15)
C5'	0.041 (2)	0.055 (2)	0.044 (2)	0.0241 (18)	0.0193 (17)	0.0271 (19)
C6'	0.0374 (19)	0.055 (2)	0.0371 (19)	0.0220 (17)	0.0111 (15)	0.0235 (17)
C1''	0.042 (2)	0.054 (2)	0.055 (3)	0.0127 (18)	0.0059 (19)	0.029 (2)
C2''	0.052 (2)	0.044 (2)	0.056 (3)	0.0180 (18)	0.027 (2)	0.0305 (19)

Geometric parameters (Å, º) top

Br1—C2'	1.887 (4)	C7—C8	1.377 (7)
Br2—C4'	1.895 (4)	C7—H7	0.9300
O1—C9B	1.344 (4)	C8—C9	1.389 (6)
O1—C2	1.497 (5)	C8—H8	0.9300
O2—C4	1.219 (5)	C9—C9A	1.379 (6)
O3—C5	1.210 (5)	C9—H9	0.9300
N1—C1'	1.374 (5)	C9A—C9B	1.451 (5)
N1—C3	1.461 (5)	C1'—C2'	1.394 (5)
N1—H1	0.8600	C1'—C6'	1.400 (5)
C2—C2''	1.514 (5)	C2'—C3'	1.379 (5)
C2—C1''	1.525 (6)	C3'—C4'	1.392 (5)
C2—C3	1.556 (5)	C3'—H3'	0.9300
C3—C3A	1.501 (5)	C4'—C5'	1.372 (6)
C3—H3	0.9800	C5'—C6'	1.391 (6)
C3A—C9B	1.360 (5)	C5'—H5'	0.9300
C3A—C4	1.436 (5)	C6'—H6'	0.9300
C4—C5	1.552 (5)	C1''—H1A	0.9600
C5—C5A	1.496 (5)	C1''—H1B	0.9600
C5A—C6	1.387 (5)	C1''—H1C	0.9600
C5A—C9A	1.406 (5)	C2''—H2A	0.9600
C6—C7	1.382 (6)	C2''—H2B	0.9600
C6—H6	0.9300	C2''—H2C	0.9600

C9B—O1—C2	107.1 (3)	C9A—C9—H9	120.0
C1'—N1—C3	125.9 (3)	C8—C9—H9	120.0
C1'—N1—H1	117.0	C9—C9A—C5A	119.9 (4)
C3—N1—H1	117.0	C9—C9A—C9B	122.9 (3)
O1—C2—C2''	106.1 (3)	C5A—C9A—C9B	117.2 (3)
O1—C2—C1''	106.1 (3)	O1—C9B—C3A	114.0 (3)
C2''—C2—C1''	112.7 (3)	O1—C9B—C9A	119.7 (3)
O1—C2—C3	104.0 (3)	C3A—C9B—C9A	126.2 (3)
C2''—C2—C3	116.4 (3)	N1—C1'—C2'	119.9 (3)
C1''—C2—C3	110.5 (3)	N1—C1'—C6'	123.5 (3)
N1—C3—C3A	106.9 (3)	C2'—C1'—C6'	116.6 (3)
N1—C3—C2	114.7 (3)	C3'—C2'—C1'	123.2 (3)
C3A—C3—C2	100.7 (3)	C3'—C2'—Br1	118.3 (3)
N1—C3—H3	111.3	C1'—C2'—Br1	118.5 (3)
C3A—C3—H3	111.3	C2'—C3'—C4'	118.5 (3)
C2—C3—H3	111.3	C2'—C3'—H3'	120.8
C9B—C3A—C4	121.3 (3)	C4'—C3'—H3'	120.8
C9B—C3A—C3	108.9 (3)	C5'—C4'—C3'	120.3 (3)
C4—C3A—C3	129.6 (3)	C5'—C4'—Br2	120.6 (3)
O2—C4—C3A	125.6 (4)	C3'—C4'—Br2	119.0 (3)
O2—C4—C5	118.8 (3)	C4'—C5'—C6'	120.3 (4)
C3A—C4—C5	115.6 (3)	C4'—C5'—H5'	119.8
O3—C5—C5A	122.3 (4)	C6'—C5'—H5'	119.8
O3—C5—C4	118.7 (4)	C5'—C6'—C1'	121.0 (4)
C5A—C5—C4	119.0 (3)	C5'—C6'—H6'	119.5
C6—C5A—C9A	119.5 (4)	C1'—C6'—H6'	119.5
C6—C5A—C5	120.3 (3)	C2—C1''—H1A	109.5
C9A—C5A—C5	120.3 (3)	C2—C1''—H1B	109.5
C7—C6—C5A	119.9 (4)	H1A—C1''—H1B	109.5
C7—C6—H6	120.0	C2—C1''—H1C	109.5
C5A—C6—H6	120.0	H1A—C1''—H1C	109.5
C8—C7—C6	120.5 (4)	H1B—C1''—H1C	109.5
C8—C7—H7	119.7	C2—C2''—H2A	109.5
C6—C7—H7	119.7	C2—C2''—H2B	109.5
C7—C8—C9	120.2 (4)	H2A—C2''—H2B	109.5
C7—C8—H8	119.9	C2—C2''—H2C	109.5
C9—C8—H8	119.9	H2A—C2''—H2C	109.5
C9A—C9—C8	119.9 (4)	H2B—C2''—H2C	109.5

C9B—O1—C2—C2''	143.2 (3)	C8—C9—C9A—C5A	−0.8 (6)
C9B—O1—C2—C1''	−96.7 (3)	C8—C9—C9A—C9B	179.1 (4)
C9B—O1—C2—C3	19.9 (4)	C6—C5A—C9A—C9	2.0 (6)
C1'—N1—C3—C3A	−154.9 (4)	C5—C5A—C9A—C9	−178.1 (4)
C1'—N1—C3—C2	94.4 (4)	C6—C5A—C9A—C9B	−177.9 (4)
O1—C2—C3—N1	92.0 (3)	C5—C5A—C9A—C9B	2.1 (5)
C2''—C2—C3—N1	−24.3 (5)	C2—O1—C9B—C3A	−8.8 (4)
C1''—C2—C3—N1	−154.5 (3)	C2—O1—C9B—C9A	172.6 (3)
O1—C2—C3—C3A	−22.4 (3)	C4—C3A—C9B—O1	178.5 (3)
C2''—C2—C3—C3A	−138.7 (3)	C3—C3A—C9B—O1	−6.9 (4)
C1''—C2—C3—C3A	91.1 (4)	C4—C3A—C9B—C9A	−3.0 (6)
N1—C3—C3A—C9B	−101.7 (4)	C3—C3A—C9B—C9A	171.6 (3)
C2—C3—C3A—C9B	18.4 (4)	C9—C9A—C9B—O1	1.7 (6)
N1—C3—C3A—C4	72.3 (5)	C5A—C9A—C9B—O1	−178.5 (3)
C2—C3—C3A—C4	−167.6 (4)	C9—C9A—C9B—C3A	−176.7 (4)
C9B—C3A—C4—O2	178.0 (4)	C5A—C9A—C9B—C3A	3.1 (6)
C3—C3A—C4—O2	4.7 (7)	C3—N1—C1'—C2'	166.3 (3)
C9B—C3A—C4—C5	−2.1 (5)	C3—N1—C1'—C6'	−14.0 (6)
C3—C3A—C4—C5	−175.4 (3)	N1—C1'—C2'—C3'	179.8 (3)
O2—C4—C5—O3	7.7 (6)	C6'—C1'—C2'—C3'	0.1 (5)
C3A—C4—C5—O3	−172.1 (4)	N1—C1'—C2'—Br1	−2.3 (5)
O2—C4—C5—C5A	−173.3 (4)	C6'—C1'—C2'—Br1	178.0 (3)
C3A—C4—C5—C5A	6.8 (5)	C1'—C2'—C3'—C4'	−1.1 (6)
O3—C5—C5A—C6	−8.0 (6)	Br1—C2'—C3'—C4'	−179.0 (3)
C4—C5—C5A—C6	173.1 (4)	C2'—C3'—C4'—C5'	1.3 (6)
O3—C5—C5A—C9A	172.0 (4)	C2'—C3'—C4'—Br2	179.9 (3)
C4—C5—C5A—C9A	−6.9 (5)	C3'—C4'—C5'—C6'	−0.4 (6)
C9A—C5A—C6—C7	−2.1 (6)	Br2—C4'—C5'—C6'	−179.1 (3)
C5—C5A—C6—C7	177.9 (4)	C4'—C5'—C6'—C1'	−0.6 (6)
C5A—C6—C7—C8	1.2 (7)	N1—C1'—C6'—C5'	−179.0 (4)
C6—C7—C8—C9	0.0 (7)	C2'—C1'—C6'—C5'	0.7 (6)
C7—C8—C9—C9A	−0.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.98	2.64	3.347 (6)	129
C1′′—H1A···O2ⁱ	0.96	2.67	3.389 (6)	132

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₅Br₂NO₃
M_r	477.15
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.1430 (3), 11.2584 (4), 11.4742 (5)
α, β, γ (°)	112.073 (2), 95.546 (2), 108.696 (2)
V (Å³)	894.70 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.55
Crystal size (mm)	0.31 × 0.28 × 0.16

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.272, 0.490
No. of measured, independent and observed [I > 2σ(I)] reflections	9784, 4099, 3610
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.139, 1.09
No. of reflections	4070
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −1.49

Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.98	2.64	3.347 (6)	129
C1''—H1A···O2ⁱ	0.96	2.67	3.389 (6)	132

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

This work received partial support from CNPq, CAPES, FAPEAL, FAPERJ, IM-INOFAR, CTPETRO and FINEP.

References

Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Dos Santos, A. F., Ferraz, P. A. L., De Abreu, F. C., Chiari, E., Goulart, M. O. F. & Sant'Ana, A. E. G. (2001). Planta Med. 67, 92–93. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hillard, E. A., de Abreu, F. C., Ferreira, D. C. M., Jaouen, G., Goulart, M. O. F. & Amatore, C. (2008). Chem. Commun. pp. 2612–2628. Web of Science CrossRef Google Scholar
Lima, N. M. F., Correia, C. S., Ferraz, P. A. L., Pinto, A. V., Pinto, M. C. R. F., Sant'Ana, A. E. G. & Goulart, M. O. F. (2002). J. Braz. Chem. Soc. 13, 822–829. CrossRef CAS Google Scholar
Lima, N. M. F., Correia, C. S., Leon, L. L., Machado, G. M. C., Madeira, M. F., Santana, A. E. G. & Goulart, M. O. F. (2004). Mem. Inst. Oswaldo Cruz, 99, 757–761. Web of Science CrossRef PubMed CAS Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet Vol. 276, 307–326, New York: Academic Press. Google Scholar
Pinto, A. V., Neves-Pinto, C., Pinto, M. C. F. R., Santa-Rita, R. M., Pezzella, C. & De Castro, S. L. (1997). Arzneim. Forsch. 47, 74–79. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Silva Júnior, E. N. da, de Souza, M. C. B. V., Fernades, M. C., Menna-Barreto, R. F. S., Pinto, A. V., Pinto, M. C. F. R., Lopes, F. A., De Simone, C. A., Andrade, C. K. Z., Ferreira, V. F. & De Castro, S. L. (2008). Bioorg. Med. Chem. 16, 5030–5038. Web of Science PubMed Google Scholar
Silva Júnior, E. N. da, de Souza, M. C. B. V., Pinto, A. V., Pinto, M. C. F. R., Goulart, M. O. F., Pessoa, C., Costa-Lotufo, L., Montenegro, R. C., Moraes, M. O. & Ferreira, V. F. (2007). Bioorg. Med. Chem. 15, 7035–7041. Web of Science PubMed 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2348

doi:10.1107/S1600536808034545

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-(2,4-Di­bromo­anilino)-2,2-di­methyl-2,3-di­hydro­naphtho[1,2-b]furan-4,5-dione: a new substituted aryl­amino nor-β-lapachone derivative

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3-(2,4-Dibromoanilino)-2,2-dimethyl-2,3-dihydronaphtho[1,2-b]furan-4,5-dione: a new substituted arylamino nor-β-lapachone derivative