Diethyl 7,8-dibromo-4,11-dioxo-11b,11c-dihydro-5H,10H-2-oxa-3a,4a,10a,11a-tetra­azabenz[f]indeno[2,1,7,7a-ija]azulene-11b,11c-dicarboxyl­ate

Chen, Y.; She, N.

doi:10.1107/S160053680903284X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2252

doi:10.1107/S160053680903284X

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Diethyl 7,8-dibromo-4,11-dioxo-11b,11c-dihydro-5H,10H-2-oxa-3a,4a,10a,11a-tetraazabenz[f]indeno[2,1,7,7a-ija]azulene-11b,11c-dicarboxylate

Yan Chen ^a and Nengfang She ^a ^*

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: wuhanshe@126.com

(Received 7 August 2009; accepted 18 August 2009; online 26 August 2009)

The title compound, C₂₀H₂₀Br₂N₄O₇, is an intermediate for molecular clips. The seven- and six-membered rings have chair conformations, while the five-membered rings adopt envelope conformations. In the crystal structure, weak C—H⋯O and C—H⋯Br interactions link the molecules into a three-dimensional network. The ethoxy and ethyl groups are disordered over two orientations, with occupancy ratios of 0.735 (16):0.265 (16) and 0.51 (2):0.49 (2), respectively.

Related literature

For general background, see: Burnett et al. (2003 ). For a related structure, see: Wu et al. (2002 ). For ring-puckering parameters, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₂₀Br₂N₄O₇
M_r = 588.22
Monoclinic, P 2₁ /c
a = 12.4679 (10) Å
b = 15.1505 (13) Å
c = 11.5383 (10) Å
β = 90.189 (1)°
V = 2179.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.77 mm⁻¹
T = 292 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: none
18344 measured reflections
4736 independent reflections
2983 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.134
S = 0.91
4736 reflections
349 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯O2ⁱ	0.97	2.51	3.353 (4)	146
C17—H17A⋯Br1ⁱⁱ	0.97	2.94	3.625 (10)	129
C8—H8B⋯O2ⁱⁱⁱ	0.97	2.39	3.324 (4)	161
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680903284X/hk2753sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903284X/hk2753Isup2.hkl

checkCIF report

Comment top

Diethoxycarbonyl glycoluril bearing a range of electron withdrawing functional groups on its convex face is an important building block for both molecular and supramolecular chemistry (Burnett et al., 2003). The title compound derived from diethoxycarbonyl glycoluril is an important intermediate for methylene-bridged glycoluril dimers, and we report herein its crystal structure.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. The seven-membered ring B (N1/N2/C1/C6-C8/c11) is not planar, having total puckering amplitude, Q_T, of 2.878 (2) Å (Cremer & Pople, 1975), and resembles chair conformation. Rings C (N1/N3/C9/C11/C15) and D (N2/N4/C10/C11/C15) adopt envelope conformations with atoms N1 and N4 displaced by -0.208 (3) and -0.174 (3) Å from the planes of the other ring atoms, respectively, while ring E (O7/N3/N4/C15/C19/C20) is not planar, having total puckering amplitude, Q_T, of 0.429 (2) Å and adopts chair conformation [ϕ = -90.18 (3) and θ = 91.16 (3) °] (Cremer & Pople, 1975).

In the crystal structure, weak C-H···O and C-H···Br interactions link the molecules into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Burnett et al. (2003). For a related structure, see: Wu et al. (2002). For ring-puckering parameters, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized according to a literature method (Wu et al., 2002). Crystals suitable for X-ray analysis were obtained by slow evaporation of a dichloride methane solution at 283 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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. A partial packing diagram. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Diethyl 7,8-dibromo-4,11-dioxo-11b,11c-dihydro-5H,10H-2-oxa-3a,4a,10a,11a-tetraazabenz[f]indeno[2,1,7,7a-ija]azulene-11b,11c-dicarboxylate top

Crystal data top

C₂₀H₂₀Br₂N₄O₇	F(000) = 1176
M_r = 588.22	D_x = 1.793 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5213 reflections
a = 12.4679 (10) Å	θ = 2.2–26.1°
b = 15.1505 (13) Å	µ = 3.77 mm⁻¹
c = 11.5383 (10) Å	T = 292 K
β = 90.189 (1)°	Block, colorless
V = 2179.5 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	2983 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.097
Graphite monochromator	θ_max = 27.0°, θ_min = 2.1°
ϕ and ω scans	h = −15→15
18344 measured reflections	k = −19→19
4736 independent reflections	l = −14→13

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.08P)²] where P = (F_o² + 2F_c²)/3
4736 reflections	(Δ/σ)_max < 0.001
349 parameters	Δρ_max = 1.00 e Å⁻³
30 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₂₀H₂₀Br₂N₄O₇	V = 2179.5 (3) Å³
M_r = 588.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.4679 (10) Å	µ = 3.77 mm⁻¹
b = 15.1505 (13) Å	T = 292 K
c = 11.5383 (10) Å	0.30 × 0.20 × 0.20 mm
β = 90.189 (1)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	2983 reflections with I > 2σ(I)
18344 measured reflections	R_int = 0.097
4736 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	30 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 0.91	Δρ_max = 1.00 e Å⁻³
4736 reflections	Δρ_min = −0.59 e Å⁻³
349 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	Occ. (<1)
Br1	−0.39306 (3)	0.14276 (3)	0.75601 (4)	0.06508 (19)
Br2	−0.31776 (4)	0.30716 (4)	0.57266 (4)	0.0716 (2)
O1	−0.01869 (19)	−0.05766 (16)	0.7742 (2)	0.0470 (7)
O2	0.1247 (2)	0.18343 (17)	0.4670 (2)	0.0461 (6)
O3	0.3227 (3)	0.2018 (2)	0.8002 (3)	0.0737 (10)
O4	0.2543 (5)	0.1138 (5)	0.9343 (4)	0.0491 (16)	0.735 (16)
O4'	0.2838 (13)	0.0817 (11)	0.9206 (11)	0.053 (4)	0.265 (16)
O5	0.3918 (3)	0.0190 (3)	0.7638 (4)	0.1048 (15)
O6	0.3624 (2)	−0.0744 (3)	0.6229 (3)	0.0823 (11)
O7	0.10231 (19)	−0.05214 (17)	0.4804 (2)	0.0465 (6)
N1	0.0940 (2)	0.05941 (18)	0.8063 (2)	0.0342 (6)
N2	0.1467 (2)	0.16772 (18)	0.6633 (2)	0.0344 (6)
N3	0.1438 (2)	−0.04468 (18)	0.6808 (3)	0.0375 (7)
N4	0.2148 (2)	0.06373 (19)	0.5477 (2)	0.0362 (7)
C1	−0.0639 (3)	0.1581 (2)	0.7972 (3)	0.0368 (8)
C2	−0.1724 (3)	0.1369 (2)	0.8074 (3)	0.0429 (9)
H2	−0.1937	0.0938	0.8599	0.052*
C3	−0.2483 (3)	0.1793 (3)	0.7405 (3)	0.0434 (9)
C4	−0.2182 (3)	0.2441 (3)	0.6642 (3)	0.0453 (9)
C5	−0.1106 (3)	0.2646 (2)	0.6516 (3)	0.0407 (8)
H5	−0.0903	0.3077	0.5988	0.049*
C6	−0.0329 (3)	0.2218 (2)	0.7163 (3)	0.0368 (8)
C7	0.0170 (3)	0.1112 (3)	0.8718 (3)	0.0423 (9)
H7A	0.0555	0.1545	0.9177	0.051*
H7B	−0.0206	0.0725	0.9249	0.051*
C8	0.0838 (3)	0.2443 (2)	0.6985 (3)	0.0381 (8)
H8A	0.0895	0.2897	0.6396	0.046*
H8B	0.1131	0.2679	0.7700	0.046*
C9	0.0625 (3)	−0.0180 (2)	0.7541 (3)	0.0358 (8)
C10	0.1571 (3)	0.1427 (2)	0.5517 (3)	0.0345 (8)
C11	0.1813 (3)	0.1016 (2)	0.7450 (3)	0.0352 (8)
C12	0.2663 (3)	0.1435 (3)	0.8275 (3)	0.0487 (10)
C13	0.3325 (7)	0.1493 (6)	1.0189 (6)	0.070 (3)	0.735 (16)
H13A	0.3212	0.2121	1.0303	0.084*	0.735 (16)
H13B	0.4052	0.1402	0.9917	0.084*	0.735 (16)
C13'	0.3735 (18)	0.0999 (19)	1.0039 (17)	0.081 (7)	0.265 (16)
H13C	0.3752	0.1621	1.0236	0.097*	0.265 (16)
H13D	0.4417	0.0841	0.9695	0.097*	0.265 (16)
C14	0.3146 (8)	0.1006 (8)	1.1289 (7)	0.106 (4)	0.735 (16)
H14A	0.2406	0.1055	1.1507	0.128*	0.735 (16)
H14B	0.3590	0.1253	1.1888	0.128*	0.735 (16)
H14C	0.3327	0.0395	1.1182	0.128*	0.735 (16)
C14'	0.354 (3)	0.045 (3)	1.112 (2)	0.165 (17)	0.265 (16)
H14D	0.2780	0.0423	1.1272	0.198*	0.265 (16)
H14E	0.3899	0.0710	1.1769	0.198*	0.265 (16)
H14F	0.3804	−0.0140	1.1001	0.198*	0.265 (16)
C15	0.2217 (2)	0.0256 (2)	0.6629 (3)	0.0344 (8)
C16	0.3359 (3)	−0.0087 (3)	0.6886 (4)	0.0492 (10)
C17	0.4520 (7)	−0.1364 (8)	0.6416 (14)	0.050 (3)	0.51 (2)
H17A	0.4337	−0.1946	0.6128	0.060*	0.51 (2)
H17B	0.4693	−0.1408	0.7234	0.060*	0.51 (2)
C17'	0.4760 (10)	−0.0973 (16)	0.6529 (15)	0.082 (6)	0.49 (2)
H17C	0.4787	−0.1386	0.7171	0.098*	0.49 (2)
H17D	0.5164	−0.0449	0.6735	0.098*	0.49 (2)
C18	0.5452 (7)	−0.0986 (11)	0.5752 (14)	0.066 (4)	0.51 (2)
H18A	0.5265	−0.0941	0.4947	0.079*	0.51 (2)
H18B	0.6064	−0.1366	0.5838	0.079*	0.51 (2)
H18C	0.5622	−0.0410	0.6049	0.079*	0.51 (2)
C18'	0.5196 (12)	−0.1389 (17)	0.5435 (14)	0.096 (6)	0.49 (2)
H18D	0.4778	−0.1901	0.5242	0.115*	0.49 (2)
H18E	0.5930	−0.1559	0.5558	0.115*	0.49 (2)
H18F	0.5158	−0.0971	0.4811	0.115*	0.49 (2)
C19	0.1211 (3)	−0.1018 (2)	0.5829 (3)	0.0459 (9)
H19A	0.1812	−0.1414	0.5707	0.055*
H19B	0.0584	−0.1375	0.5997	0.055*
C20	0.1918 (3)	0.0019 (3)	0.4536 (3)	0.0435 (9)
H20A	0.1773	0.0346	0.3830	0.052*
H20B	0.2541	−0.0350	0.4403	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0421 (2)	0.0827 (4)	0.0705 (3)	−0.0127 (2)	0.0010 (2)	−0.0028 (2)
Br2	0.0526 (3)	0.0970 (4)	0.0652 (3)	0.0130 (2)	−0.0028 (2)	0.0176 (3)
O1	0.0421 (14)	0.0383 (14)	0.0606 (18)	−0.0069 (11)	0.0073 (12)	0.0001 (12)
O2	0.0572 (15)	0.0466 (15)	0.0344 (15)	0.0013 (12)	−0.0013 (12)	0.0038 (12)
O3	0.070 (2)	0.074 (2)	0.077 (2)	−0.0353 (17)	−0.0222 (17)	0.0031 (18)
O4	0.045 (3)	0.067 (4)	0.035 (3)	0.001 (2)	−0.016 (2)	−0.003 (2)
O4'	0.031 (6)	0.088 (9)	0.039 (6)	0.006 (6)	−0.004 (5)	−0.006 (6)
O5	0.058 (2)	0.129 (4)	0.127 (3)	0.027 (2)	−0.050 (2)	−0.051 (3)
O6	0.0556 (18)	0.107 (3)	0.084 (2)	0.0454 (18)	−0.0168 (17)	−0.028 (2)
O7	0.0470 (14)	0.0474 (15)	0.0451 (16)	0.0019 (12)	−0.0088 (12)	−0.0125 (12)
N1	0.0360 (14)	0.0362 (15)	0.0303 (15)	−0.0013 (12)	0.0016 (12)	−0.0024 (13)
N2	0.0391 (15)	0.0336 (15)	0.0305 (16)	−0.0023 (12)	0.0009 (12)	−0.0027 (12)
N3	0.0387 (15)	0.0336 (16)	0.0401 (17)	−0.0002 (12)	−0.0002 (13)	−0.0040 (13)
N4	0.0375 (14)	0.0399 (16)	0.0311 (16)	0.0030 (12)	−0.0010 (12)	−0.0026 (13)
C1	0.0437 (19)	0.0347 (19)	0.0320 (19)	0.0005 (15)	0.0056 (15)	−0.0098 (15)
C2	0.049 (2)	0.042 (2)	0.038 (2)	−0.0012 (17)	0.0076 (17)	−0.0068 (17)
C3	0.0372 (18)	0.047 (2)	0.046 (2)	−0.0059 (16)	0.0066 (16)	−0.0110 (18)
C4	0.0426 (19)	0.050 (2)	0.043 (2)	0.0057 (17)	−0.0009 (16)	−0.0114 (18)
C5	0.049 (2)	0.0367 (19)	0.037 (2)	0.0009 (16)	0.0057 (16)	−0.0064 (16)
C6	0.0452 (19)	0.0327 (18)	0.033 (2)	−0.0001 (15)	0.0026 (15)	−0.0093 (15)
C7	0.050 (2)	0.046 (2)	0.032 (2)	−0.0033 (17)	0.0086 (16)	−0.0054 (17)
C8	0.0440 (18)	0.0330 (18)	0.037 (2)	−0.0029 (15)	0.0020 (16)	−0.0044 (15)
C9	0.0354 (17)	0.0367 (19)	0.035 (2)	0.0035 (15)	−0.0008 (14)	0.0037 (15)
C10	0.0327 (16)	0.0355 (19)	0.035 (2)	−0.0065 (14)	−0.0005 (14)	−0.0015 (16)
C11	0.0332 (16)	0.0411 (19)	0.0311 (19)	−0.0037 (14)	−0.0038 (14)	−0.0035 (15)
C12	0.044 (2)	0.060 (3)	0.042 (2)	−0.0079 (19)	−0.0106 (18)	−0.006 (2)
C13	0.071 (4)	0.069 (5)	0.070 (5)	−0.005 (4)	−0.039 (4)	−0.001 (4)
C13'	0.092 (11)	0.080 (11)	0.071 (10)	−0.014 (8)	−0.004 (8)	−0.021 (8)
C14	0.119 (7)	0.133 (9)	0.066 (6)	0.014 (7)	−0.041 (5)	0.008 (5)
C14'	0.166 (19)	0.165 (19)	0.165 (19)	0.001 (10)	−0.012 (10)	−0.006 (10)
C15	0.0315 (16)	0.0384 (19)	0.0334 (19)	0.0004 (14)	−0.0028 (14)	−0.0037 (15)
C16	0.0362 (19)	0.060 (3)	0.051 (3)	0.0025 (18)	−0.0016 (18)	0.007 (2)
C17	0.045 (5)	0.046 (6)	0.059 (8)	0.004 (4)	−0.002 (4)	−0.004 (5)
C17'	0.049 (8)	0.081 (12)	0.115 (11)	0.036 (7)	−0.037 (8)	−0.039 (10)
C18	0.043 (5)	0.089 (10)	0.065 (9)	0.014 (5)	0.009 (5)	0.011 (7)
C18'	0.057 (8)	0.104 (14)	0.127 (15)	0.035 (8)	−0.016 (8)	−0.013 (10)
C19	0.045 (2)	0.037 (2)	0.056 (3)	−0.0023 (16)	0.0008 (18)	−0.0112 (19)
C20	0.048 (2)	0.048 (2)	0.034 (2)	0.0065 (17)	0.0040 (16)	−0.0097 (17)

Geometric parameters (Å, º) top

Br1—C3	1.896 (3)	C13'—C14'	1.522 (10)
Br2—C4	1.887 (4)	C13'—H13C	0.9700
O4—C13	1.479 (6)	C13'—H13D	0.9700
O4'—C13'	1.498 (10)	C14—H14A	0.9600
C1—C2	1.396 (5)	C14—H14B	0.9600
C1—C6	1.399 (5)	C14—H14C	0.9600
C1—C7	1.503 (5)	C14'—H14D	0.9600
C2—C3	1.378 (5)	C14'—H14E	0.9600
C2—H2	0.9300	C14'—H14F	0.9600
C3—C4	1.372 (6)	C15—N4	1.451 (4)
C4—C5	1.386 (5)	C15—N3	1.457 (4)
C5—C6	1.382 (5)	C15—C16	1.544 (5)
C5—H5	0.9300	C16—O5	1.188 (5)
C6—C8	1.509 (5)	C16—O6	1.294 (5)
C7—N1	1.453 (4)	C17—O6	1.475 (8)
C7—H7A	0.9700	C17—C18	1.507 (9)
C7—H7B	0.9700	C17—H17A	0.9700
C8—N2	1.459 (4)	C17—H17B	0.9700
C8—H8A	0.9700	C17'—O6	1.497 (8)
C8—H8B	0.9700	C17'—C18'	1.514 (10)
C9—O1	1.199 (4)	C17'—H17C	0.9700
C9—N1	1.376 (4)	C17'—H17D	0.9700
C9—N3	1.383 (4)	C18—H18A	0.9600
C10—O2	1.223 (4)	C18—H18B	0.9600
C10—N2	1.349 (4)	C18—H18C	0.9600
C10—N4	1.396 (4)	C18'—H18D	0.9600
C11—N2	1.440 (4)	C18'—H18E	0.9600
C11—N1	1.450 (4)	C18'—H18F	0.9600
C11—C12	1.558 (5)	C19—O7	1.421 (5)
C11—C15	1.575 (5)	C19—N3	1.451 (5)
C12—O3	1.173 (5)	C19—H19A	0.9700
C12—O4	1.321 (6)	C19—H19B	0.9700
C12—O4'	1.441 (10)	C20—O7	1.419 (4)
C13—C14	1.485 (8)	C20—N4	1.462 (5)
C13—H13A	0.9700	C20—H20A	0.9700
C13—H13B	0.9700	C20—H20B	0.9700

C12—O4—C13	114.5 (5)	O3—C12—C11	123.3 (4)
C12—O4'—C13'	118.0 (14)	O4—C12—C11	110.7 (4)
C16—O6—C17	126.8 (7)	O4'—C12—C11	107.0 (6)
C16—O6—C17'	106.6 (6)	O4—C13—C14	106.4 (5)
C20—O7—C19	111.1 (3)	O4—C13—H13A	110.4
C9—N1—C11	112.1 (3)	C14—C13—H13A	110.4
C9—N1—C7	120.0 (3)	O4—C13—H13B	110.4
C11—N1—C7	120.9 (3)	C14—C13—H13B	110.4
C10—N2—C11	113.5 (3)	H13A—C13—H13B	108.6
C10—N2—C8	122.9 (3)	O4'—C13'—C14'	107.5 (13)
C11—N2—C8	122.1 (3)	O4'—C13'—H13C	110.2
C9—N3—C19	120.6 (3)	C14'—C13'—H13C	110.2
C9—N3—C15	111.4 (3)	O4'—C13'—H13D	110.2
C19—N3—C15	117.0 (3)	C14'—C13'—H13D	110.2
C10—N4—C15	109.9 (3)	H13C—C13'—H13D	108.5
C10—N4—C20	118.3 (3)	C13'—C14'—H14D	109.5
C15—N4—C20	115.9 (3)	C13'—C14'—H14E	109.5
C2—C1—C6	119.0 (3)	H14D—C14'—H14E	109.5
C2—C1—C7	119.5 (3)	C13'—C14'—H14F	109.5
C6—C1—C7	121.5 (3)	H14D—C14'—H14F	109.5
C3—C2—C1	120.6 (4)	H14E—C14'—H14F	109.5
C3—C2—H2	119.7	N4—C15—N3	112.6 (3)
C1—C2—H2	119.7	N4—C15—C16	111.2 (3)
C4—C3—C2	120.3 (3)	N3—C15—C16	109.9 (3)
C4—C3—Br1	122.1 (3)	N4—C15—C11	104.0 (3)
C2—C3—Br1	117.6 (3)	N3—C15—C11	103.6 (2)
C3—C4—C5	119.7 (4)	C16—C15—C11	115.3 (3)
C3—C4—Br2	122.7 (3)	O5—C16—O6	123.3 (4)
C5—C4—Br2	117.6 (3)	O5—C16—C15	124.0 (4)
C6—C5—C4	121.0 (4)	O6—C16—C15	112.6 (3)
C6—C5—H5	119.5	O6—C17—C18	105.6 (7)
C4—C5—H5	119.5	O6—C17—H17A	110.6
C5—C6—C1	119.3 (3)	C18—C17—H17A	110.6
C5—C6—C8	119.7 (3)	O6—C17—H17B	110.6
C1—C6—C8	121.0 (3)	C18—C17—H17B	110.6
N1—C7—C1	113.6 (3)	H17A—C17—H17B	108.8
N1—C7—H7A	108.9	O6—C17'—C18'	104.3 (7)
C1—C7—H7A	108.9	O6—C17'—H17C	110.9
N1—C7—H7B	108.9	C18'—C17'—H17C	110.9
C1—C7—H7B	108.9	O6—C17'—H17D	110.9
H7A—C7—H7B	107.7	C18'—C17'—H17D	110.9
N2—C8—C6	112.2 (3)	H17C—C17'—H17D	108.9
N2—C8—H8A	109.2	C17'—C18'—H18D	109.5
C6—C8—H8A	109.2	C17'—C18'—H18E	109.5
N2—C8—H8B	109.2	H18D—C18'—H18E	109.5
C6—C8—H8B	109.2	C17'—C18'—H18F	109.5
H8A—C8—H8B	107.9	H18D—C18'—H18F	109.5
O1—C9—N1	125.6 (3)	H18E—C18'—H18F	109.5
O1—C9—N3	126.3 (3)	O7—C19—N3	111.3 (3)
N1—C9—N3	107.9 (3)	O7—C19—H19A	109.4
O2—C10—N2	126.0 (3)	N3—C19—H19A	109.4
O2—C10—N4	125.1 (3)	O7—C19—H19B	109.4
N2—C10—N4	108.9 (3)	N3—C19—H19B	109.4
N2—C11—N1	113.7 (3)	H19A—C19—H19B	108.0
N2—C11—C12	108.6 (3)	O7—C20—N4	111.1 (3)
N1—C11—C12	113.1 (3)	O7—C20—H20A	109.4
N2—C11—C15	102.2 (3)	N4—C20—H20A	109.4
N1—C11—C15	102.3 (3)	O7—C20—H20B	109.4
C12—C11—C15	116.6 (3)	N4—C20—H20B	109.4
O3—C12—O4	125.3 (4)	H20A—C20—H20B	108.0
O3—C12—O4'	127.0 (7)

C6—C1—C2—C3	−1.2 (5)	N3—C9—N1—C7	168.9 (3)
C7—C1—C2—C3	179.5 (3)	N2—C11—N1—C9	94.8 (3)
C1—C2—C3—C4	−1.0 (5)	C12—C11—N1—C9	−140.8 (3)
C1—C2—C3—Br1	177.5 (3)	C15—C11—N1—C9	−14.6 (3)
C2—C3—C4—C5	2.2 (6)	N2—C11—N1—C7	−56.0 (4)
Br1—C3—C4—C5	−176.2 (3)	C12—C11—N1—C7	68.4 (4)
C2—C3—C4—Br2	−178.3 (3)	C15—C11—N1—C7	−165.4 (3)
Br1—C3—C4—Br2	3.2 (5)	C1—C7—N1—C9	−72.5 (4)
C3—C4—C5—C6	−1.1 (6)	C1—C7—N1—C11	76.0 (4)
Br2—C4—C5—C6	179.4 (3)	O2—C10—N2—C11	173.0 (3)
C4—C5—C6—C1	−1.2 (5)	N4—C10—N2—C11	−9.2 (4)
C4—C5—C6—C8	178.6 (3)	O2—C10—N2—C8	6.8 (5)
C2—C1—C6—C5	2.3 (5)	N4—C10—N2—C8	−175.4 (3)
C7—C1—C6—C5	−178.5 (3)	N1—C11—N2—C10	−107.8 (3)
C2—C1—C6—C8	−177.5 (3)	C12—C11—N2—C10	125.4 (3)
C7—C1—C6—C8	1.7 (5)	C15—C11—N2—C10	1.7 (3)
C2—C1—C7—N1	117.2 (4)	N1—C11—N2—C8	58.5 (4)
C6—C1—C7—N1	−62.0 (4)	C12—C11—N2—C8	−68.3 (4)
C5—C6—C8—N2	−120.8 (3)	C15—C11—N2—C8	168.0 (3)
C1—C6—C8—N2	59.0 (4)	C6—C8—N2—C10	86.8 (4)
N2—C11—C12—O3	−28.4 (5)	C6—C8—N2—C11	−78.2 (4)
N1—C11—C12—O3	−155.6 (4)	O1—C9—N3—C19	27.9 (5)
C15—C11—C12—O3	86.2 (5)	N1—C9—N3—C19	−156.0 (3)
N2—C11—C12—O4	142.1 (5)	O1—C9—N3—C15	170.8 (3)
N1—C11—C12—O4	14.9 (6)	N1—C9—N3—C15	−13.1 (4)
C15—C11—C12—O4	−103.3 (5)	O7—C19—N3—C9	93.6 (4)
N2—C11—C12—O4'	169.3 (9)	O7—C19—N3—C15	−47.3 (4)
N1—C11—C12—O4'	42.0 (9)	N4—C15—N3—C9	−107.8 (3)
C15—C11—C12—O4'	−76.1 (9)	C16—C15—N3—C9	127.6 (3)
O3—C12—O4—C13	−10.4 (9)	C11—C15—N3—C9	3.9 (3)
O4'—C12—O4—C13	92.9 (17)	N4—C15—N3—C19	36.5 (4)
C11—C12—O4—C13	179.4 (5)	C16—C15—N3—C19	−88.1 (4)
C12—O4—C13—C14	−173.3 (7)	C11—C15—N3—C19	148.2 (3)
O3—C12—O4'—C13'	10.1 (19)	O2—C10—N4—C15	−169.0 (3)
O4—C12—O4'—C13'	−86 (2)	N2—C10—N4—C15	13.2 (3)
C11—C12—O4'—C13'	171.6 (13)	O2—C10—N4—C20	−32.8 (5)
C12—O4'—C13'—C14'	162 (2)	N2—C10—N4—C20	149.4 (3)
N2—C11—C15—N4	5.9 (3)	N3—C15—N4—C10	99.8 (3)
N1—C11—C15—N4	123.9 (3)	C16—C15—N4—C10	−136.3 (3)
C12—C11—C15—N4	−112.2 (3)	C11—C15—N4—C10	−11.6 (3)
N2—C11—C15—N3	−111.9 (3)	N3—C15—N4—C20	−37.5 (4)
N1—C11—C15—N3	6.1 (3)	C16—C15—N4—C20	86.4 (4)
C12—C11—C15—N3	130.0 (3)	C11—C15—N4—C20	−148.9 (3)
N2—C11—C15—C16	128.0 (3)	O7—C20—N4—C10	−83.8 (4)
N1—C11—C15—C16	−114.0 (3)	O7—C20—N4—C15	49.8 (4)
C12—C11—C15—C16	9.8 (4)	O5—C16—O6—C17	12.8 (8)
N4—C15—C16—O5	117.6 (5)	C15—C16—O6—C17	−163.9 (5)
N3—C15—C16—O5	−117.0 (5)	O5—C16—O6—C17'	−6.2 (13)
C11—C15—C16—O5	−0.5 (6)	C15—C16—O6—C17'	177.0 (11)
N4—C15—C16—O6	−65.6 (4)	C18—C17—O6—C16	−93.3 (16)
N3—C15—C16—O6	59.7 (4)	C18—C17—O6—C17'	−48.3 (18)
C11—C15—C16—O6	176.3 (3)	C18'—C17'—O6—C16	−153.5 (19)
O1—C9—N1—C11	−166.1 (3)	C18'—C17'—O6—C17	62.7 (17)
N3—C9—N1—C11	17.8 (4)	N4—C20—O7—C19	−59.7 (4)
O1—C9—N1—C7	−15.0 (5)	N3—C19—O7—C20	58.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O2ⁱ	0.97	2.51	3.353 (4)	146
C17—H17A···Br1ⁱⁱ	0.97	2.94	3.625 (10)	129
C8—H8B···O2ⁱⁱⁱ	0.97	2.39	3.324 (4)	161

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀Br₂N₄O₇
M_r	588.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	12.4679 (10), 15.1505 (13), 11.5383 (10)
β (°)	90.189 (1)
V (Å³)	2179.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.77
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18344, 4736, 2983
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.134, 0.91
No. of reflections	4736
No. of parameters	349
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.59

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O2ⁱ	0.97	2.51	3.353 (4)	145.8
C17—H17A···Br1ⁱⁱ	0.97	2.94	3.625 (10)	128.9
C8—H8B···O2ⁱⁱⁱ	0.97	2.39	3.324 (4)	160.6

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

Acknowledgements

The authors are grateful to the Central China Normal University, and Professor Wu Anxin for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, C. A., Lagona, J., Wu, A., Shaw, J. A., Coady, D., Fettinger, J. C., Day, A. I. & Isaacs, L. (2003). Tetrahedron, 59, 1961–1970. Web of Science CSD CrossRef CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, A., Chakraborty, A., Witt, D., Lagona, J., Damkaci, F., Ofori, M. A., Chiles, J. K., Fettinger, J. C. & Isaacs, L. (2002). J. Org. Chem. 67, 5817–5830. Web of Science CSD CrossRef PubMed CAS Google Scholar

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Volume 65| Part 9| September 2009| Page o2252

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

Di­ethyl 7,8-di­bromo-4,11-dioxo-11b,11c-di­hydro-5H,10H-2-oxa-3a,4a,10a,11a-tetra­azabenz[f]indeno[2,1,7,7a-ija]azulene-11b,11c-di­carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Diethyl 7,8-dibromo-4,11-dioxo-11b,11c-dihydro-5H,10H-2-oxa-3a,4a,10a,11a-tetraazabenz[f]indeno[2,1,7,7a-ija]azulene-11b,11c-dicarboxylate