(4S,5S)-2-(2-Bromo­phen­yl)-1,3-dioxolane-4,5-dicarboxamide

Liu, H.; Wang, D.-C.; Xu, W.; Yang, Z.; Gai, T.

doi:10.1107/S1600536809010009

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o841

doi:10.1107/S1600536809010009

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(4S,5S)-2-(2-Bromophenyl)-1,3-dioxolane-4,5-dicarboxamide

Hua-quan Liu,^a De-Cai Wang,^a ^* Wei Xu,^a Zheng Yang ^a and Tao Gai ^a

^aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dcwang@njut.edu.cn

(Received 16 March 2009; accepted 18 March 2009; online 25 March 2009)

The asymmetric unit of the title compound, C₁₁H₁₁BrN₂O₄, contains two crystallographically independent molecules in which the bromophenyl rings are oriented at dihedral angles of 39.28 (3)°. The dioxolane rings adopt envelope conformations. Intramolecular N—H⋯O hydrogen bonds result in the formation of four five-membered rings, having planar and envelope conformations. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link molecules into chains along the b axis, forming R₂²(8) ring motifs.

Related literature

For the use of similar compounds in the synthesis of platinum based anti-tumour agents and in organic syntheses, see: Kim et al. (1994 ); Pandey et al. (1997 ). For bond-length data, see: Allen et al. (1987 ). For ring motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₁BrN₂O₄
M_r = 315.12
Monoclinic, P 2₁
a = 9.4150 (19) Å
b = 14.458 (3) Å
c = 9.6170 (19) Å
β = 111.14 (3)°
V = 1221.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.38 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.552, T_max = 0.729
4504 measured reflections
4256 independent reflections
2669 reflections with I > 2σ(I)
R_int = 0.061
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.181
S = 1.00
4256 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.82 e Å⁻³
Absolute structure: Flack (1983 ), 1758 Friedel pairs
Flack parameter: 0.00 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1	0.86	2.25	2.657 (12)	109
N2—H2B⋯O2	0.86	2.27	2.660 (12)	107
N3—H3B⋯O8ⁱ	0.86	2.28	3.123 (14)	167
N3—H3C⋯O5	0.86	2.32	2.684 (14)	106
N4—H4B⋯O7ⁱⁱ	0.86	2.05	2.876 (11)	160
N4—H4C⋯O6	0.86	2.26	2.672 (11)	110
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010009/hk2643sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010009/hk2643Isup2.hkl

checkCIF report

Comment top

Antitumor platinum drug is one kind of the most effective anticancer agents currently available. (2S,3S)-Diethyl 2,3-O-alkyltartrate analogues are starting materials for the syntheses of platinum complexes with antitumor activity (Kim et al., 1994), and are also important intermediates in organic syntheses (Pandey et al., 1997). As part of our studies on the syntheses and characterizations of these compounds, we have synthesized the title compound and reported herein its crystal structure.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and A' (C12-C17) are, of course, planar and they are oriented at a dihedral angle of A/A' = 39.28 (3)°. Rings B (O1/O2/C7-C9) and B' (O5/O6/C18-C20) adopt envelope conformations with C7 and C18 atoms displaced by 0.503 (3) and -0.589 (3) Å from the planes of the other ring atoms, rspectively. The intramolecular N-H···O hydrogen bonds (Table 1) result in the formations of four five-membered rings: C (O1/N1/C9/C10/H1B), D (O2/N2/C8/C11/H2B) and C' (O5/N3/C19/C21/H3C), D' (O6/N4/C20/C22/H4C). Ring D is planar, while rings C, C' and D' have envelope conformations with atoms O1, O5 and O6 displaced by 0.223 (3), -0.530 (3) and -0.304 (3) Å, respectively, from the planes of the other ring atoms.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into chains along the b-axis, forming R₂²(8) ring motifs (Fig. 2) (Bernstein et al., 1995). in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Kim et al. (1994); Pandey et al. (1997). For bond-length data, see: Allen et al. (1987). For ring motifs, see: Bernstein et al. (1995).

Experimental top

For the preparation of the title compound, 2-bromobenzaldehyde (300 mg, 1.62 mmol), (2S,3S)-diethyltartrate (434 mg, 2.11 mmol) and cyclohexane (10 ml) were placed in a round-bottomed flask, and 4-methylbenzenesulfonic acid (30 mg) was added. The flask was fitted with a water-distributor. The mixture was heated under reflux for 3 h. The reaction mixture was cooled to room temperature, and then transferred into a separatory funnel, washed with water (200 ml) and extracted with acetate (200 ml). The organic phase was distilled under pressure, and the residual was dissolved in anhydrous ethanol (50 ml). Then, a current of dry ammonia was passed through the reaction mixture at room temperature for about 4 h. The reaction mixture was then added dropwise to a vigorously stirred water (600 ml). The resulting colorless precipitate was obtained by filtration and dried in vacuo (Kim et al., 1994). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution after two weeks.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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) and 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 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

(4S,5S)-2-(2-Bromophenyl)-1,3-dioxolane-4,5-dicarboxamide top

Crystal data top

C₁₁H₁₁BrN₂O₄	F(000) = 632
M_r = 315.12	D_x = 1.714 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 9.4150 (19) Å	θ = 10–13°
b = 14.458 (3) Å	µ = 3.38 mm⁻¹
c = 9.6170 (19) Å	T = 294 K
β = 111.14 (3)°	Block, colorless
V = 1221.0 (5) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2669 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
Graphite monochromator	θ_max = 26.0°, θ_min = 2.3°
ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = −10→17
T_min = 0.552, T_max = 0.729	l = −11→11
4504 measured reflections	3 standard reflections every 120 min
4256 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.181	w = 1/[σ²(F_o²) + (0.1P)² + 1.54P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4256 reflections	Δρ_max = 0.54 e Å⁻³
325 parameters	Δρ_min = −0.82 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1758 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

Crystal data top

C₁₁H₁₁BrN₂O₄	V = 1221.0 (5) Å³
M_r = 315.12	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 9.4150 (19) Å	µ = 3.38 mm⁻¹
b = 14.458 (3) Å	T = 294 K
c = 9.6170 (19) Å	0.20 × 0.10 × 0.10 mm
β = 111.14 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2669 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.061
T_min = 0.552, T_max = 0.729	3 standard reflections every 120 min
4504 measured reflections	intensity decay: 1%
4256 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.181	Δρ_max = 0.54 e Å⁻³
S = 1.00	Δρ_min = −0.82 e Å⁻³
4256 reflections	Absolute structure: Flack (1983), 1758 Friedel pairs
325 parameters	Absolute structure parameter: 0.00 (2)
0 restraints

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	0.02596 (15)	0.99788 (7)	0.97303 (14)	0.0608 (5)
Br2	0.51991 (15)	0.59675 (7)	0.96846 (14)	0.0584 (4)
O1	0.2071 (7)	0.8476 (4)	1.2310 (7)	0.0342 (15)
O2	0.3547 (9)	0.7557 (5)	1.1503 (8)	0.045 (2)
O3	0.5492 (8)	0.9264 (5)	1.5118 (7)	0.0425 (17)
O4	0.5063 (11)	0.6732 (6)	1.5238 (9)	0.072 (3)
O5	0.1786 (8)	0.3598 (6)	0.8478 (8)	0.0402 (19)
O6	0.3262 (6)	0.4292 (4)	0.7424 (6)	0.0289 (14)
O7	−0.0743 (8)	0.2608 (5)	0.5162 (8)	0.051 (2)
O8	−0.0128 (9)	0.5151 (6)	0.4748 (10)	0.077 (3)
N1	0.3494 (10)	1.0032 (7)	1.3501 (9)	0.054 (2)
H1A	0.3872	1.0569	1.3798	0.065*
H1B	0.2618	0.9983	1.2798	0.065*
N2	0.3894 (12)	0.6010 (7)	1.3088 (9)	0.065 (3)
H2A	0.3936	0.5487	1.3527	0.078*
H2B	0.3480	0.6046	1.2133	0.078*
N3	0.1299 (12)	0.2007 (8)	0.6938 (12)	0.083 (4)
H3B	0.1123	0.1461	0.6557	0.100*
H3C	0.2075	0.2103	0.7737	0.100*
N4	0.2056 (10)	0.5835 (6)	0.5937 (10)	0.058 (3)
H4B	0.1804	0.6354	0.5475	0.070*
H4C	0.2946	0.5768	0.6609	0.070*
C1	−0.1253 (13)	0.8539 (9)	0.7843 (12)	0.054 (3)
H1C	−0.1973	0.8994	0.7406	0.065*
C2	−0.1452 (15)	0.7645 (9)	0.7283 (14)	0.063 (3)
H2C	−0.2335	0.7490	0.6491	0.076*
C3	−0.0347 (14)	0.6989 (9)	0.7897 (12)	0.060 (3)
H3A	−0.0477	0.6397	0.7492	0.072*
C4	0.0952 (12)	0.7193 (8)	0.9104 (12)	0.045 (3)
H4A	0.1685	0.6738	0.9501	0.055*
C5	0.1177 (10)	0.8071 (7)	0.9733 (10)	0.032 (2)
C6	0.0023 (11)	0.8736 (7)	0.9049 (11)	0.041 (2)
C7	0.2506 (12)	0.8300 (7)	1.1051 (11)	0.042 (3)
H7A	0.3017	0.8846	1.0846	0.051*
C8	0.4385 (13)	0.7664 (7)	1.3091 (12)	0.043 (3)
H8A	0.5406	0.7913	1.3284	0.051*
C9	0.3383 (11)	0.8363 (7)	1.3586 (10)	0.033 (2)
H9A	0.3110	0.8091	1.4389	0.040*
C10	0.4257 (11)	0.9281 (7)	1.4125 (10)	0.035 (2)
C11	0.4458 (12)	0.6747 (7)	1.3868 (11)	0.040 (2)
C12	0.6632 (12)	0.4664 (8)	1.1863 (12)	0.047 (3)
H12A	0.7377	0.5119	1.2195	0.057*
C13	0.6768 (12)	0.3799 (8)	1.2638 (11)	0.047 (3)
H13A	0.7629	0.3679	1.3475	0.056*
C14	0.5657 (12)	0.3166 (9)	1.2157 (12)	0.050 (3)
H14A	0.5721	0.2619	1.2687	0.060*
C15	0.4429 (12)	0.3328 (7)	1.0882 (11)	0.042 (2)
H15A	0.3687	0.2872	1.0542	0.051*
C16	0.4242 (11)	0.4149 (7)	1.0072 (10)	0.038 (2)
C17	0.5378 (11)	0.4786 (7)	1.0634 (10)	0.038 (2)
C18	0.2854 (10)	0.4319 (7)	0.8716 (10)	0.035 (2)
H18A	0.2392	0.4915	0.8789	0.042*
C19	0.0858 (10)	0.3643 (7)	0.6949 (11)	0.033 (2)
H19A	−0.0053	0.4007	0.6842	0.040*
C20	0.1849 (12)	0.4189 (7)	0.6234 (10)	0.041 (3)
H20A	0.1984	0.3824	0.5433	0.049*
C21	0.0373 (12)	0.2699 (7)	0.6293 (12)	0.041 (3)
C22	0.1035 (12)	0.5114 (7)	0.5599 (10)	0.039 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0828 (10)	0.0392 (9)	0.0483 (8)	0.0150 (7)	0.0090 (7)	0.0055 (7)
Br2	0.0742 (9)	0.0320 (8)	0.0488 (8)	−0.0102 (7)	−0.0022 (7)	0.0053 (7)
O1	0.041 (3)	0.031 (4)	0.028 (4)	0.001 (3)	0.009 (3)	−0.002 (3)
O2	0.070 (5)	0.033 (5)	0.028 (4)	0.010 (4)	0.011 (4)	−0.001 (3)
O3	0.061 (4)	0.026 (4)	0.031 (4)	−0.005 (3)	0.006 (3)	0.001 (3)
O4	0.113 (7)	0.032 (5)	0.035 (4)	0.013 (4)	−0.016 (4)	−0.006 (4)
O5	0.048 (4)	0.043 (5)	0.023 (4)	−0.007 (4)	0.005 (3)	0.000 (3)
O6	0.034 (3)	0.031 (4)	0.014 (3)	0.007 (3)	−0.001 (2)	0.000 (3)
O7	0.060 (4)	0.034 (5)	0.032 (4)	−0.001 (3)	−0.016 (3)	−0.005 (3)
O8	0.073 (5)	0.043 (6)	0.068 (6)	−0.003 (4)	−0.031 (5)	0.019 (4)
N1	0.063 (5)	0.030 (5)	0.045 (5)	−0.002 (5)	−0.010 (4)	−0.011 (5)
N2	0.121 (8)	0.030 (5)	0.024 (5)	−0.022 (6)	0.001 (5)	0.002 (5)
N3	0.091 (7)	0.033 (6)	0.071 (7)	0.008 (6)	−0.038 (6)	−0.003 (6)
N4	0.054 (5)	0.042 (7)	0.056 (6)	−0.003 (5)	−0.007 (4)	0.023 (5)
C1	0.060 (5)	0.062 (6)	0.035 (5)	0.007 (5)	0.012 (4)	0.007 (5)
C2	0.071 (6)	0.059 (6)	0.046 (6)	−0.016 (5)	0.006 (5)	0.006 (5)
C3	0.086 (6)	0.048 (6)	0.040 (5)	−0.012 (5)	0.015 (4)	−0.010 (5)
C4	0.062 (5)	0.032 (5)	0.037 (5)	−0.003 (4)	0.012 (4)	0.001 (4)
C5	0.034 (4)	0.033 (5)	0.029 (4)	−0.007 (4)	0.012 (3)	0.006 (4)
C6	0.054 (5)	0.038 (5)	0.030 (5)	0.006 (4)	0.015 (4)	0.008 (4)
C7	0.067 (7)	0.018 (6)	0.038 (6)	0.004 (5)	0.016 (5)	0.001 (5)
C8	0.064 (7)	0.015 (6)	0.033 (6)	0.001 (5)	−0.002 (5)	−0.003 (5)
C9	0.052 (6)	0.027 (6)	0.022 (5)	0.004 (4)	0.015 (4)	0.007 (4)
C10	0.052 (6)	0.033 (7)	0.019 (5)	0.004 (5)	0.010 (4)	0.002 (4)
C11	0.058 (6)	0.024 (6)	0.025 (5)	0.007 (5)	0.000 (4)	−0.005 (4)
C12	0.053 (5)	0.044 (6)	0.040 (5)	0.002 (4)	0.009 (4)	−0.003 (4)
C13	0.052 (5)	0.049 (6)	0.030 (5)	0.008 (4)	0.004 (4)	0.001 (4)
C14	0.058 (5)	0.050 (6)	0.034 (5)	0.004 (4)	0.008 (4)	0.007 (4)
C15	0.062 (5)	0.025 (5)	0.031 (5)	0.001 (4)	0.007 (4)	−0.003 (4)
C16	0.058 (5)	0.027 (5)	0.023 (4)	0.004 (4)	0.009 (4)	−0.003 (4)
C17	0.055 (5)	0.021 (5)	0.031 (5)	0.003 (4)	0.006 (4)	−0.004 (4)
C18	0.049 (5)	0.031 (6)	0.022 (5)	−0.006 (5)	0.009 (4)	−0.003 (4)
C19	0.033 (5)	0.025 (6)	0.036 (6)	−0.005 (4)	0.008 (4)	−0.007 (5)
C20	0.071 (7)	0.021 (6)	0.024 (5)	0.020 (5)	0.009 (5)	0.000 (4)
C21	0.048 (6)	0.028 (6)	0.038 (6)	−0.001 (5)	0.003 (5)	0.007 (5)
C22	0.059 (6)	0.030 (7)	0.019 (5)	0.003 (5)	0.002 (4)	0.005 (4)

Geometric parameters (Å, º) top

Br1—C6	1.897 (11)	C2—H2C	0.9300
Br2—C17	1.915 (10)	C3—C4	1.381 (15)
O1—C9	1.402 (11)	C3—H3A	0.9300
O1—C7	1.434 (11)	C4—C5	1.389 (15)
O2—C7	1.414 (12)	C4—H4A	0.9300
O2—C8	1.453 (12)	C5—C6	1.422 (13)
O3—C10	1.210 (11)	C5—C7	1.462 (14)
O4—C11	1.232 (12)	C7—H7A	0.9800
O5—C18	1.409 (11)	C8—C11	1.511 (14)
O5—C19	1.416 (11)	C8—C9	1.568 (14)
O6—C20	1.416 (11)	C8—H8A	0.9800
O6—C18	1.427 (11)	C9—C10	1.549 (14)
O7—C21	1.217 (11)	C9—H9A	0.9800
O8—C22	1.107 (11)	C12—C17	1.348 (13)
N1—C10	1.321 (12)	C12—C13	1.437 (16)
N1—H1A	0.8600	C12—H12A	0.9300
N1—H1B	0.8600	C13—C14	1.341 (15)
N2—C11	1.301 (13)	C13—H13A	0.9300
N2—H2A	0.8600	C14—C15	1.369 (14)
N2—H2B	0.8600	C14—H14A	0.9300
N3—C21	1.324 (13)	C15—C16	1.395 (14)
N3—H3B	0.8600	C15—H15A	0.9300
N3—H3C	0.8600	C16—C17	1.367 (14)
N4—C22	1.375 (13)	C16—C18	1.497 (12)
N4—H4B	0.8600	C18—H18A	0.9800
N4—H4C	0.8600	C19—C21	1.504 (14)
C1—C6	1.366 (14)	C19—C20	1.559 (15)
C1—C2	1.386 (18)	C19—H19A	0.9800
C1—H1C	0.9300	C20—C22	1.552 (13)
C2—C3	1.374 (17)	C20—H20A	0.9800

C9—O1—C7	106.8 (7)	C10—C9—H9A	109.8
C7—O2—C8	107.2 (8)	C8—C9—H9A	109.8
C18—O5—C19	105.7 (7)	O3—C10—N1	125.8 (9)
C20—O6—C18	103.7 (7)	O3—C10—C9	119.4 (8)
C10—N1—H1A	120.0	N1—C10—C9	114.6 (8)
C10—N1—H1B	120.0	O4—C11—N2	122.5 (10)
H1A—N1—H1B	120.0	O4—C11—C8	117.7 (9)
C11—N2—H2A	120.0	N2—C11—C8	119.8 (9)
C11—N2—H2B	120.0	C17—C12—C13	117.1 (10)
H2A—N2—H2B	120.0	C17—C12—H12A	121.5
C21—N3—H3B	120.0	C13—C12—H12A	121.5
C21—N3—H3C	120.0	C14—C13—C12	120.2 (10)
H3B—N3—H3C	120.0	C14—C13—H13A	119.9
C22—N4—H4B	120.0	C12—C13—H13A	119.9
C22—N4—H4C	120.0	C13—C14—C15	119.6 (11)
H4B—N4—H4C	120.0	C13—C14—H14A	120.2
C6—C1—C2	118.7 (12)	C15—C14—H14A	120.2
C6—C1—H1C	120.7	C14—C15—C16	122.8 (11)
C2—C1—H1C	120.7	C14—C15—H15A	118.6
C3—C2—C1	120.1 (12)	C16—C15—H15A	118.6
C3—C2—H2C	120.0	C17—C16—C15	115.4 (9)
C1—C2—H2C	120.0	C17—C16—C18	123.1 (9)
C2—C3—C4	121.2 (12)	C15—C16—C18	121.4 (9)
C2—C3—H3A	119.4	C12—C17—C16	124.8 (10)
C4—C3—H3A	119.4	C12—C17—Br2	115.7 (8)
C3—C4—C5	120.7 (11)	C16—C17—Br2	119.4 (7)
C3—C4—H4A	119.6	O5—C18—O6	103.9 (7)
C5—C4—H4A	119.6	O5—C18—C16	111.5 (8)
C4—C5—C6	116.5 (9)	O6—C18—C16	109.3 (8)
C4—C5—C7	122.2 (9)	O5—C18—H18A	110.7
C6—C5—C7	121.3 (9)	O6—C18—H18A	110.7
C1—C6—C5	122.8 (11)	C16—C18—H18A	110.7
C1—C6—Br1	116.7 (8)	O5—C19—C21	112.0 (9)
C5—C6—Br1	120.4 (8)	O5—C19—C20	103.8 (7)
O2—C7—O1	104.7 (8)	C21—C19—C20	114.5 (9)
O2—C7—C5	112.1 (8)	O5—C19—H19A	108.8
O1—C7—C5	110.9 (8)	C21—C19—H19A	108.8
O2—C7—H7A	109.7	C20—C19—H19A	108.8
O1—C7—H7A	109.7	O6—C20—C22	114.5 (8)
C5—C7—H7A	109.7	O6—C20—C19	103.5 (7)
O2—C8—C11	109.7 (8)	C22—C20—C19	108.8 (8)
O2—C8—C9	103.3 (8)	O6—C20—H20A	110.0
C11—C8—C9	109.9 (9)	C22—C20—H20A	110.0
O2—C8—H8A	111.2	C19—C20—H20A	110.0
C11—C8—H8A	111.2	O7—C21—N3	123.2 (10)
C9—C8—H8A	111.2	O7—C21—C19	120.4 (9)
O1—C9—C10	112.7 (8)	N3—C21—C19	116.1 (9)
O1—C9—C8	104.3 (7)	O8—C22—N4	124.0 (10)
C10—C9—C8	110.4 (8)	O8—C22—C20	123.2 (10)
O1—C9—H9A	109.8	N4—C22—C20	110.9 (8)

C6—C1—C2—C3	−2.9 (18)	C17—C12—C13—C14	−1.8 (16)
C1—C2—C3—C4	2.1 (19)	C12—C13—C14—C15	3.3 (17)
C2—C3—C4—C5	0.0 (19)	C13—C14—C15—C16	−2.5 (18)
C3—C4—C5—C6	−1.2 (15)	C14—C15—C16—C17	0.3 (16)
C3—C4—C5—C7	177.3 (10)	C14—C15—C16—C18	−177.5 (10)
C2—C1—C6—C5	1.7 (16)	C13—C12—C17—C16	−0.5 (17)
C2—C1—C6—Br1	178.3 (9)	C13—C12—C17—Br2	177.4 (8)
C4—C5—C6—C1	0.4 (15)	C15—C16—C17—C12	1.2 (16)
C7—C5—C6—C1	−178.2 (10)	C18—C16—C17—C12	179.0 (10)
C4—C5—C6—Br1	−176.1 (8)	C15—C16—C17—Br2	−176.6 (7)
C7—C5—C6—Br1	5.3 (13)	C18—C16—C17—Br2	1.2 (14)
C8—O2—C7—O1	−33.6 (10)	C19—O5—C18—O6	−40.6 (9)
C8—O2—C7—C5	−153.9 (9)	C19—O5—C18—C16	−158.2 (8)
C9—O1—C7—O2	38.4 (9)	C20—O6—C18—O5	44.5 (8)
C9—O1—C7—C5	159.5 (8)	C20—O6—C18—C16	163.6 (8)
C4—C5—C7—O2	4.6 (14)	C17—C16—C18—O5	−173.1 (9)
C6—C5—C7—O2	−176.9 (8)	C15—C16—C18—O5	4.5 (14)
C4—C5—C7—O1	−111.9 (10)	C17—C16—C18—O6	72.7 (12)
C6—C5—C7—O1	66.6 (11)	C15—C16—C18—O6	−109.7 (10)
C7—O2—C8—C11	133.8 (9)	C18—O5—C19—C21	144.8 (9)
C7—O2—C8—C9	16.6 (10)	C18—O5—C19—C20	20.7 (10)
C7—O1—C9—C10	92.9 (9)	C18—O6—C20—C22	88.1 (9)
C7—O1—C9—C8	−26.9 (9)	C18—O6—C20—C19	−30.1 (9)
O2—C8—C9—O1	6.4 (10)	O5—C19—C20—O6	6.1 (9)
C11—C8—C9—O1	−110.6 (8)	C21—C19—C20—O6	−116.3 (8)
O2—C8—C9—C10	−114.9 (9)	O5—C19—C20—C22	−116.0 (8)
C11—C8—C9—C10	128.1 (9)	C21—C19—C20—C22	121.6 (9)
O1—C9—C10—O3	−172.2 (8)	O5—C19—C21—O7	158.6 (10)
C8—C9—C10—O3	−56.0 (11)	C20—C19—C21—O7	−83.5 (13)
O1—C9—C10—N1	12.7 (12)	O5—C19—C21—N3	−27.2 (14)
C8—C9—C10—N1	128.9 (9)	C20—C19—C21—N3	90.7 (13)
O2—C8—C11—O4	−176.2 (9)	O6—C20—C22—O8	−173.5 (11)
C9—C8—C11—O4	−63.3 (13)	C19—C20—C22—O8	−58.3 (14)
O2—C8—C11—N2	3.9 (15)	O6—C20—C22—N4	21.5 (12)
C9—C8—C11—N2	116.9 (11)	C19—C20—C22—N4	136.7 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1	0.86	2.25	2.657 (12)	109
N2—H2B···O2	0.86	2.27	2.660 (12)	107
N3—H3B···O8ⁱ	0.86	2.28	3.123 (14)	167
N3—H3C···O5	0.86	2.32	2.684 (14)	106
N4—H4B···O7ⁱⁱ	0.86	2.05	2.876 (11)	160
N4—H4C···O6	0.86	2.26	2.672 (11)	110

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁BrN₂O₄
M_r	315.12
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	294
a, b, c (Å)	9.4150 (19), 14.458 (3), 9.6170 (19)
β (°)	111.14 (3)
V (Å³)	1221.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.38
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.552, 0.729
No. of measured, independent and observed [I > 2σ(I)] reflections	4504, 4256, 2669
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.181, 1.00
No. of reflections	4256
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.82
Absolute structure	Flack (1983), 1758 Friedel pairs
Absolute structure parameter	0.00 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1	0.86	2.25	2.657 (12)	109
N2—H2B···O2	0.86	2.27	2.660 (12)	107
N3—H3B···O8ⁱ	0.86	2.28	3.123 (14)	167
N3—H3C···O5	0.86	2.32	2.684 (14)	106
N4—H4B···O7ⁱⁱ	0.86	2.05	2.876 (11)	160
N4—H4C···O6	0.86	2.26	2.672 (11)	110

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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