Crystal structure of methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-di­bromo-8-oxo-1-oxa­spiro­[4.5]deca-2,6,9-triene-3-car­boxyl­ate

Martins, L.J.; Simoni, D. de A.; Aparicio, R.; Coelho, F.

doi:10.1107/S1600536814024763

organic compounds

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages o1275-o1276

doi:10.1107/S1600536814024763

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Crystal structure of methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-dibromo-8-oxo-1-oxaspiro[4.5]deca-2,6,9-triene-3-carboxylate

Lucimara Julio Martins,^a Deborah de Alencar Simoni,^b Ricardo Aparicio ^c ^* and Fernando Coelho ^a

^aLaboratory of Synthesis of Natural Products and Drugs, Institute of Chemistry, University of Campinas, PO Box 6154 - 13083-970, Campinas, SP, Brazil, ^bLaboratory of Single Crystal X-Ray Diffraction, Institute of Chemistry, University of Campinas, PO Box 6154 - 13083-970, Campinas, SP, Brazil, and ^cLaboratory of Structural Biology and Crystallography, Institute of Chemistry, University of Campinas, PO Box 6154 - 13083-970, Campinas, SP, Brazil
^*Correspondence e-mail: aparicio@iqm.unicamp.br

Edited by P. C. Healy, Griffith University, Australia (Received 14 October 2014; accepted 11 November 2014; online 21 November 2014)

The title compound, C₁₈H₁₂Br₂O₆, was synthesized from Morita–Baylis–Hillman adducts. It incorporates the brominated spiro-hexadienone moiety typically exhibited by compounds of this class that exhibit biological activity. Both the brominated cyclohexadienone and the central five-membered rings are nearly planar (r.m.s. deviations of 0.044 and 0.016 Å, respectively), being almost perpendicularly oriented [interplanar angle = 89.47 (5)°]. With respect to the central five-membered ring, the brominated cyclohexadienone ring, the benzodioxol ring and the carboxylate fragment make C—O—C—C, O—C—C—C and C—C—C—O dihedral angles of −122.11 (8), −27.20 (11) and −8.40 (12)°, respectively. An intramolecular C—H⋯O hydrogen bond occurs. In the crystal, molecules are linked by non-classical C—H⋯O and C—H⋯Br hydrogen bonds resulting in a molecular packing in which the brominated rings are in a head-to-head orientation, forming well marked planes parallel to the b axis.

Keywords: Single-crystal X-ray study; spiro-hexadienone structure; Morita–Baylis–Hillman adducts.

CCDC reference: 1033626

1. Related literature

For compounds that contain a spiro-hexadienone moiety in their structures, related biological activities and examples of brominated spiro-hexadienones, see: König & Wright (1993 ); Lou (2012 ); Sorek et al. (2009 ). For strategies for the synthesis of spiro-hexadienones from Morita–Baylis–Hillman aducts, see: Martins et al. (2014 ); Barontini et al. (2013 ).

2. Experimental

2.1. Crystal data

C₁₈H₁₂Br₂O₆
M_r = 484.10
Triclinic, $[P \overline 1]$
a = 8.1929 (13) Å
b = 8.4811 (14) Å
c = 12.761 (2) Å
α = 84.485 (4)°
β = 80.007 (5)°
γ = 78.077 (4)°
V = 852.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 4.79 mm⁻¹
T = 100 K
0.32 × 0.17 × 0.16 mm

2.2. Data collection

Bruker APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.309, T_max = 0.515
27788 measured reflections
7098 independent reflections
6288 reflections with I > 2σ(I)
R_int = 0.017

2.3. Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.047
S = 1.02
7098 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O5ⁱ	0.95	2.61	3.4272 (13)	144
C7—H7⋯O5	0.95	2.34	2.9441 (13)	121
C10—H10A⋯O1ⁱⁱ	0.99	2.55	3.3995 (13)	143
C12—H12A⋯Br1ⁱⁱⁱ	0.99	2.96	3.9411 (12)	173
C12—H12A⋯O1ⁱⁱⁱ	0.99	2.53	3.0852 (13)	116
C13—H13⋯O2^iv	0.95	2.63	3.3909 (13)	137
C16—H16C⋯O5^v	0.98	2.59	3.2434 (14)	124
C17—H17⋯Br1^vi	0.95	3.03	3.9069 (11)	153
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) -x+2, -y+2, -z+1; (iii) x, y-1, z+1; (iv) -x+1, -y+2, -z+2; (v) -x+3, -y+1, -z+2; (vi) x, y-1, z.

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011 ) and SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2003 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1033626

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814024763/hg5413sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024763/hg5413Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814024763/hg5413Isup4.cdx

Supporting information file. DOI: 10.1107/S1600536814024763/hg5413Isup4.cml

checkCIF report

Introduction top

Compounds containing a spiro-hexadienone moiety typically exhibit biological activity, also sharing a structural architecture observed in some natural products (König & Wright, 1993; Sorek et al., 2009). In view of the importance of this class of compounds, recent efforts resulted in a new synthetic strategy, which starts from Morita-Baylis-Hillman adducts as building blocks for organic synthesis (Martins et al., 2014). Based on this methodology, it was possible to obtain a brominated spiro-hexadienone which resulted, to our knowledge, in the first report of a halogenated spiro-hexadienone crystal structure.

Experimental top

Synthesis and crystallization top

\ Methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-dibromo-8-oxo-1-oxaspiro[4.5]deca-2,6,9-\ triene-3-carboxylate was prepared from a subset of β-ketoesters following the experimental protocol recently described by Barontini et al. (2013). A separable mixture of mono- and dibrominated (in majority) derivatives in good overall yields was obtained.

After chromatographic separation, the dibrominated compounds were easily transformed into halogenated spiro-hexadienones, in three steps procedure, starting with the Morita-Baylis-Hillman adducts.

Methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-dibromo-8-oxo-1-oxaspiro[4.5]deca-2,6,9-\ triene-3-carboxylate (48 mg, 0.1 mmoL) was dissolved in absolute chloroform-D1 (1 mL), followed by stirring until total dissolution was achieved. The solution was kept in the freezer. After two weeks, the resulting material was filtered under vacuum, washed with small portions of cold chloroform and dried in a desiccator to furnish pale yellow single crystals suitable for X-ray diffraction data collection.

Refinement top

The C-bound H atoms were positioned with idealized geometry and treated as riding atoms: phenyl, methyl and methylene C—H bond lengths were 0.95, 0.98 and 0.99 Å, respectively. The isotropic displacement parameters values (U_iso(H)) were fixed at 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for all other attached H atoms.

Results and discussion top

The title compound (Fig. 1) crystallized in the space group P1 assuming a conformational structure determined by non-classical intramolecular C—H—O and intermolecular C—H—O and C—H—Br bonding (Table 1, Fig. 2). The molecule contains one six-membered (brominated ciclohexadienone) and one central five-membered rings connected by a spiro-carbon C4. The mean plane of these planar rings, C1—C2—C4—C17—C18 (r.m.s.= 0.044 Å) and C4—C10—C11—C5—O2 (r.m.s. = 0.016 Å), are almost perpendicularly oriented, making a plane-plane angle of 90.53°. With respect to the central five-membered ring, the brominated spiro-hexadienone and the benzodioxol rings make dihedral angles C5—O2—C4—C3 = -122.11 (8)° and O2—C5—C6—C14 = -27.20 (11)°, respectively, while the dihedral angle with the carboxylate fragment C10—C11—C15—O6 is -8.40 (12)°.

In the hexadienone ring of the title compound, the C2—C3, C17—C18 and C1—O1 bond lengths are 1.3351 (13), 1.3354 (13) and 1.2139 (11) Å, respectively, and the bond length between the spiro-carbon (C4) and the oxygen atom C4—O2 is 1.4684 (11) Å, similar to those reported for a related oxaspiro structure (Lou, 2012). In the latter, the plane-plane angle between the mean planes of the six-membered and the central five-membered rings in the spiro-carbon is 96.06°, slightly different from that observed in the title compound (90.53°). Further comparison also reveals different orientations of the carboxylate moiety, which makes a dihedral angle of 170.6 (1)° (C10—C11—C15—O5) in the title compound, with a corresponding angle equal to 11.3 (3)° in the related structure (Lou, 2012). This large difference is consistent with an observed C7—H7—O5 intramolecular hydrogen bond (Table 1) in the title compound, which results in a favourable conformation of the carboxylate group.

Related literature top

For compounds that contain a spiro-hexadienone moiety in their structures, related biological activities and examples of brominated spiro-hexadienones, see: König & Wright (1993); Lou (2012); Sorek et al. (2009). For strategies for the synthesis of spiro-hexadienones from Morita–Baylis–Hillman aducts, see: Martins et al. (2014); Barontini et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2003), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids.

Crystal packing of the title compound, showing hydrogen bonding interactions.

2-(2H-1,3-Benzodioxol-5-yl)-7,9-dibromo-8-oxo-1-oxaspiro[4.5]deca-2,6,9-triene-3-carboxylate top

Crystal data top

C₁₈H₁₂Br₂O₆	Z = 2
M_r = 484.10	F(000) = 476
Triclinic, P1	D_x = 1.885 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1929 (13) Å	Cell parameters from 9887 reflections
b = 8.4811 (14) Å	θ = 3.2–35.1°
c = 12.761 (2) Å	µ = 4.79 mm⁻¹
α = 84.485 (4)°	T = 100 K
β = 80.007 (5)°	Block, pale yellow
γ = 78.077 (4)°	0.32 × 0.17 × 0.16 mm
V = 852.7 (2) Å³

Data collection top

Bruker APEX CCD detector diffractometer	7098 independent reflections
Radiation source: fine-focus sealed tube	6288 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.017
phi and ω scans	θ_max = 34.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −12→12
T_min = 0.309, T_max = 0.515	k = −13→13
27788 measured reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.018	H-atom parameters constrained
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.0245P)² + 0.2583P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.003
7098 reflections	Δρ_max = 0.57 e Å⁻³
236 parameters	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₈H₁₂Br₂O₆	γ = 78.077 (4)°
M_r = 484.10	V = 852.7 (2) Å³
Triclinic, P1	Z = 2
a = 8.1929 (13) Å	Mo Kα radiation
b = 8.4811 (14) Å	µ = 4.79 mm⁻¹
c = 12.761 (2) Å	T = 100 K
α = 84.485 (4)°	0.32 × 0.17 × 0.16 mm
β = 80.007 (5)°

Data collection top

Bruker APEX CCD detector diffractometer	7098 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	6288 reflections with I > 2σ(I)
T_min = 0.309, T_max = 0.515	R_int = 0.017
27788 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 1.02	Δρ_max = 0.57 e Å⁻³
7098 reflections	Δρ_min = −0.39 e Å⁻³
236 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.81611 (2)	1.44904 (2)	0.62579 (2)	0.01782 (3)
Br2	0.72560 (2)	0.85491 (2)	0.49155 (2)	0.01638 (3)
O1	0.75814 (11)	1.20677 (9)	0.48397 (6)	0.01915 (14)
O2	0.81234 (9)	0.93071 (9)	0.86474 (5)	0.01450 (12)
O3	0.57197 (10)	0.68379 (9)	1.33065 (6)	0.01608 (13)
O4	0.81596 (9)	0.50402 (9)	1.26861 (6)	0.01609 (13)
O5	1.24024 (10)	0.67487 (10)	1.01728 (6)	0.01916 (14)
O6	1.37041 (9)	0.72220 (9)	0.84968 (6)	0.01529 (12)
C1	0.79228 (12)	1.13898 (10)	0.56785 (7)	0.01214 (14)
C2	0.83286 (12)	1.22429 (10)	0.65381 (7)	0.01222 (14)
C3	0.88062 (12)	1.14902 (11)	0.74351 (7)	0.01357 (15)
H3	0.8963	1.2114	0.7977	0.016*
C4	0.91021 (12)	0.96878 (11)	0.76100 (7)	0.01264 (15)
C5	0.91926 (12)	0.83972 (10)	0.92957 (7)	0.01135 (14)
C6	0.82769 (11)	0.79788 (10)	1.03513 (7)	0.01106 (14)
C7	0.88494 (12)	0.65586 (11)	1.09690 (7)	0.01202 (14)
H7	0.9864	0.5828	1.0731	0.014*
C8	0.78592 (12)	0.62914 (11)	1.19325 (7)	0.01182 (14)
C9	0.63896 (12)	0.73620 (11)	1.23042 (7)	0.01254 (14)
C10	1.09810 (12)	0.89627 (12)	0.77135 (7)	0.01504 (16)
H10A	1.1501	0.8183	0.7164	0.018*
H10B	1.1655	0.9820	0.7656	0.018*
C11	1.08297 (12)	0.81321 (11)	0.88176 (7)	0.01190 (14)
C12	0.66357 (14)	0.52054 (12)	1.34563 (8)	0.01708 (17)
H12A	0.6912	0.5003	1.4188	0.020*
H12B	0.5948	0.4422	1.3344	0.020*
C13	0.58111 (12)	0.87530 (11)	1.17181 (8)	0.01435 (15)
H13	0.4809	0.9486	1.1975	0.017*
C14	0.67762 (12)	0.90331 (11)	1.07223 (7)	0.01288 (15)
H14	0.6401	0.9965	1.0287	0.015*
C15	1.23289 (12)	0.72953 (11)	0.92621 (7)	0.01239 (14)
C16	1.52864 (13)	0.64225 (14)	0.88280 (9)	0.02125 (19)
H16A	1.5418	0.6880	0.9478	0.032*
H16B	1.6222	0.6580	0.8261	0.032*
H16C	1.5291	0.5265	0.8969	0.032*
C17	0.85126 (12)	0.88535 (11)	0.68028 (7)	0.01319 (15)
H17	0.8524	0.7728	0.6918	0.016*
C18	0.79718 (12)	0.96291 (10)	0.59287 (7)	0.01170 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02471 (5)	0.00997 (4)	0.01954 (5)	−0.00466 (3)	−0.00492 (4)	0.00072 (3)
Br2	0.02188 (5)	0.01408 (4)	0.01473 (4)	−0.00300 (3)	−0.00654 (3)	−0.00306 (3)
O1	0.0307 (4)	0.0153 (3)	0.0107 (3)	−0.0017 (3)	−0.0063 (3)	0.0023 (2)
O2	0.0119 (3)	0.0197 (3)	0.0100 (3)	−0.0004 (2)	−0.0030 (2)	0.0048 (2)
O3	0.0186 (3)	0.0160 (3)	0.0112 (3)	−0.0020 (2)	0.0011 (2)	0.0023 (2)
O4	0.0173 (3)	0.0147 (3)	0.0138 (3)	−0.0009 (2)	−0.0019 (2)	0.0056 (2)
O5	0.0146 (3)	0.0278 (4)	0.0125 (3)	0.0000 (3)	−0.0034 (2)	0.0045 (3)
O6	0.0106 (3)	0.0196 (3)	0.0133 (3)	0.0005 (2)	−0.0009 (2)	0.0011 (2)
C1	0.0137 (4)	0.0115 (3)	0.0101 (3)	−0.0011 (3)	−0.0008 (3)	−0.0001 (3)
C2	0.0144 (4)	0.0101 (3)	0.0119 (4)	−0.0024 (3)	−0.0017 (3)	0.0000 (3)
C3	0.0153 (4)	0.0137 (3)	0.0123 (4)	−0.0032 (3)	−0.0034 (3)	−0.0009 (3)
C4	0.0137 (4)	0.0143 (3)	0.0091 (3)	−0.0018 (3)	−0.0025 (3)	0.0023 (3)
C5	0.0129 (4)	0.0113 (3)	0.0096 (3)	−0.0011 (3)	−0.0037 (3)	0.0010 (3)
C6	0.0123 (4)	0.0117 (3)	0.0093 (3)	−0.0021 (3)	−0.0028 (3)	0.0004 (3)
C7	0.0128 (4)	0.0113 (3)	0.0114 (3)	−0.0009 (3)	−0.0024 (3)	0.0003 (3)
C8	0.0135 (4)	0.0111 (3)	0.0109 (3)	−0.0020 (3)	−0.0036 (3)	0.0012 (3)
C9	0.0139 (4)	0.0133 (3)	0.0101 (3)	−0.0028 (3)	−0.0012 (3)	−0.0001 (3)
C10	0.0131 (4)	0.0196 (4)	0.0110 (4)	−0.0014 (3)	−0.0027 (3)	0.0036 (3)
C11	0.0122 (4)	0.0133 (3)	0.0095 (3)	−0.0010 (3)	−0.0024 (3)	0.0009 (3)
C12	0.0219 (5)	0.0149 (4)	0.0127 (4)	−0.0037 (3)	0.0000 (3)	0.0027 (3)
C13	0.0139 (4)	0.0140 (4)	0.0130 (4)	0.0005 (3)	−0.0006 (3)	0.0004 (3)
C14	0.0131 (4)	0.0127 (3)	0.0116 (4)	−0.0004 (3)	−0.0026 (3)	0.0015 (3)
C15	0.0115 (4)	0.0132 (3)	0.0117 (4)	−0.0005 (3)	−0.0023 (3)	−0.0003 (3)
C16	0.0119 (4)	0.0287 (5)	0.0201 (5)	0.0015 (4)	−0.0019 (3)	0.0012 (4)
C17	0.0151 (4)	0.0114 (3)	0.0126 (4)	−0.0018 (3)	−0.0031 (3)	0.0012 (3)
C18	0.0134 (4)	0.0110 (3)	0.0108 (3)	−0.0018 (3)	−0.0025 (3)	−0.0011 (3)

Geometric parameters (Å, º) top

Br1—C2	1.8863 (9)	C6—C14	1.4001 (13)
Br2—C18	1.8887 (9)	C6—C7	1.4158 (12)
O1—C1	1.2139 (11)	C7—C8	1.3775 (13)
O2—C5	1.3772 (11)	C7—H7	0.9500
O2—C4	1.4684 (11)	C8—C9	1.3900 (13)
O3—C9	1.3721 (11)	C9—C13	1.3777 (13)
O3—C12	1.4444 (12)	C10—C11	1.5104 (13)
O4—C8	1.3746 (11)	C10—H10A	0.9900
O4—C12	1.4397 (13)	C10—H10B	0.9900
O5—C15	1.2158 (11)	C11—C15	1.4623 (13)
O6—C15	1.3520 (11)	C12—H12A	0.9900
O6—C16	1.4459 (13)	C12—H12B	0.9900
C1—C2	1.4887 (13)	C13—C14	1.4026 (13)
C1—C18	1.4904 (12)	C13—H13	0.9500
C2—C3	1.3351 (13)	C14—H14	0.9500
C3—C4	1.4985 (13)	C16—H16A	0.9800
C3—H3	0.9500	C16—H16B	0.9800
C4—C17	1.4996 (13)	C16—H16C	0.9800
C4—C10	1.5585 (14)	C17—C18	1.3354 (13)
C5—C11	1.3563 (13)	C17—H17	0.9500
C5—C6	1.4733 (12)

C5—O2—C4	109.46 (7)	C11—C10—H10A	111.3
C9—O3—C12	104.80 (7)	C4—C10—H10A	111.3
C8—O4—C12	105.13 (7)	C11—C10—H10B	111.3
C15—O6—C16	115.44 (8)	C4—C10—H10B	111.3
O1—C1—C2	122.93 (8)	H10A—C10—H10B	109.2
O1—C1—C18	122.50 (8)	C5—C11—C15	128.64 (8)
C2—C1—C18	114.57 (8)	C5—C11—C10	110.13 (8)
C3—C2—C1	123.31 (8)	C15—C11—C10	121.07 (8)
C3—C2—Br1	121.81 (7)	O4—C12—O3	106.94 (7)
C1—C2—Br1	114.87 (6)	O4—C12—H12A	110.3
C2—C3—C4	121.73 (8)	O3—C12—H12A	110.3
C2—C3—H3	119.1	O4—C12—H12B	110.3
C4—C3—H3	119.1	O3—C12—H12B	110.3
O2—C4—C3	107.32 (7)	H12A—C12—H12B	108.6
O2—C4—C17	106.47 (7)	C9—C13—C14	116.62 (9)
C3—C4—C17	114.33 (8)	C9—C13—H13	121.7
O2—C4—C10	105.43 (7)	C14—C13—H13	121.7
C3—C4—C10	111.56 (8)	C6—C14—C13	121.91 (8)
C17—C4—C10	111.13 (8)	C6—C14—H14	119.0
C11—C5—O2	112.55 (8)	C13—C14—H14	119.0
C11—C5—C6	135.58 (8)	O5—C15—O6	122.92 (9)
O2—C5—C6	111.85 (8)	O5—C15—C11	127.60 (9)
C14—C6—C7	120.45 (8)	O6—C15—C11	109.47 (8)
C14—C6—C5	117.27 (8)	O6—C16—H16A	109.5
C7—C6—C5	122.27 (8)	O6—C16—H16B	109.5
C8—C7—C6	116.53 (8)	H16A—C16—H16B	109.5
C8—C7—H7	121.7	O6—C16—H16C	109.5
C6—C7—H7	121.7	H16A—C16—H16C	109.5
O4—C8—C7	127.79 (8)	H16B—C16—H16C	109.5
O4—C8—C9	109.53 (8)	C18—C17—C4	122.64 (8)
C7—C8—C9	122.61 (8)	C18—C17—H17	118.7
O3—C9—C13	128.16 (9)	C4—C17—H17	118.7
O3—C9—C8	109.94 (8)	C17—C18—C1	122.38 (8)
C13—C9—C8	121.85 (8)	C17—C18—Br2	121.91 (7)
C11—C10—C4	102.30 (7)	C1—C18—Br2	115.70 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.95	2.61	3.4272 (13)	144
C7—H7···O5	0.95	2.34	2.9441 (13)	121
C10—H10A···O1ⁱⁱ	0.99	2.55	3.3995 (13)	143
C12—H12A···Br1ⁱⁱⁱ	0.99	2.96	3.9411 (12)	173
C12—H12A···O1ⁱⁱⁱ	0.99	2.53	3.0852 (13)	116
C13—H13···O2^iv	0.95	2.63	3.3909 (13)	137
C16—H16C···O5^v	0.98	2.59	3.2434 (14)	124
C17—H17···Br1^vi	0.95	3.03	3.9069 (11)	153
C14—H14···O2	0.95	2.36	2.6937 (12)	100

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, −y+2, −z+1; (iii) x, y−1, z+1; (iv) −x+1, −y+2, −z+2; (v) −x+3, −y+1, −z+2; (vi) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.95	2.61	3.4272 (13)	143.8
C7—H7···O5	0.95	2.34	2.9441 (13)	120.7
C10—H10A···O1ⁱⁱ	0.99	2.55	3.3995 (13)	143.4
C12—H12A···Br1ⁱⁱⁱ	0.99	2.96	3.9411 (12)	172.7
C12—H12A···O1ⁱⁱⁱ	0.99	2.53	3.0852 (13)	115.5
C13—H13···O2^iv	0.95	2.63	3.3909 (13)	136.9
C16—H16C···O5^v	0.98	2.59	3.2434 (14)	124.1
C17—H17···Br1^vi	0.95	3.03	3.9069 (11)	153.4
C14—H14···O2	0.95	2.36	2.6937 (12)	100.3

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, −y+2, −z+1; (iii) x, y−1, z+1; (iv) −x+1, −y+2, −z+2; (v) −x+3, −y+1, −z+2; (vi) x, y−1, z.

Acknowledgements

The authors acknowledge Dr Jorge Henrique Monteiro for preliminary structure refinement. This work was supported by the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP 2009/18390–4 and 2009/51602–5), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). RA is the recipient of a research grant from CNPq.

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Volume 70| Part 12| December 2014| Pages o1275-o1276

doi:10.1107/S1600536814024763

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

Crystal structure of methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-di­bromo-8-oxo-1-oxa­spiro­[4.5]deca-2,6,9-triene-3-car­boxyl­ate

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of methyl 2-(2H-1,3-benzodioxol-5-yl)-7,9-dibromo-8-oxo-1-oxaspiro[4.5]deca-2,6,9-triene-3-carboxylate