4-(4-Bromo­phen­yl)-2-methyl­amino-3-nitro-5,6,7,8-tetra­hydro-4H-chromen-5-one

Narayanan, P.; Kamalraja, J.; Perumal, P.T.; Sethusankar, K.

doi:10.1107/S1600536813012774

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages o931-o932

doi:10.1107/S1600536813012774

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4-(4-Bromophenyl)-2-methylamino-3-nitro-5,6,7,8-tetrahydro-4H-chromen-5-one

P. Narayanan,^a Jayabal Kamalraja,^b Paramasivam T. Perumal ^b and K. Sethusankar ^a ^*

^aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^bOrganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 4 May 2013; accepted 9 May 2013; online 22 May 2013)

In the title compound, C₁₆H₁₅BrN₂O₄, the six-membered carbocyclic ring of the chromene moiety adopts an envelope conformation with the disordered methylene C atom as the flap. The pyran ring is almost orthogonal to the chlorophenyl ring, making a dihedral angle of 87.11 (12)°. The amine-group N atom deviates significantly from the pyran ring [0.238 (3) Å]. The molecular structure is stabilized by an intramolecular N—H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, which generate C(8) chains running parallel to the b axis. The chains are linked by C—H⋯π interactions. The methylene-group C atom of the chromene system that is disordered, along with its attached H atoms and the H atoms on the two adjacent C atoms, has an occupancy ratio of 0.791 (7):0.209 (7).

Related literature

For the uses and biological importance of chromene, see: Ercole et al. (2009 ); Geen et al. (1996 ) Khan et al. (2010 ); Raj et al. (2010 ). For a related structure, see: Sun et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₆H₁₅BrN₂O₄
M_r = 379.18
Monoclinic, P 2₁ /n
a = 8.1114 (9) Å
b = 10.8530 (13) Å
c = 18.222 (2) Å
β = 94.399 (6)°
V = 1599.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.59 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.464, T_max = 0.523
12198 measured reflections
3130 independent reflections
2053 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.04
3130 reflections
218 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the pyran ring (C7/C8/C13/O1/C14/C15).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3	0.90 (2)	1.89 (2)	2.595 (3)	134 (2)
C2—H2⋯O4ⁱ	0.93	2.55	3.442 (4)	162
C10—H10B⋯Cg1ⁱⁱ	0.97	2.77	3.527 (3)	136
C16—H16B⋯Cg1ⁱⁱⁱ	0.96	2.73	3.606 (4)	153
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813012774/su2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012774/su2597Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813012774/su2597Isup3.cml

checkCIF report

Comment top

Chromene derivatives are very important heterocyclic compounds that have a variety of industrial, biological and chemical synthesis applications (Geen et al., 1996; Ercole et al., 2009). They exhibit a number of pharmacological activities such as anti-HIV, anti-inflammatory, anti-bacterial, anti-allergic, anti-cancer, etc. (Khan et al., 2010, Raj et al., 2010). Against this background an X-ray diffraction study of the title compound and its structural aspects are presented herein.

The title compound, Fig. 1, consists of a chromene moiety attached to a chlorophenyl ring, a nitro group and a methylamine group. The molecular structure is stabilized by an intramolecular N—H···O hydrogen bonds, which generates an S(6) ring motif (Table 1 and Fig. 1). The methylene group carbon atom C11 of the chromene moiety is disordered over two positions (C11/C11') with an occupancy ratio of 0.791 (7): 0.209 (7). The pyran ring (C7/C8/C13-C15/O1) makes a dihedral angle of 87.11 (12) ° with the cholorophenyl ring (C1–C6), indicating that they are almost orthogonal.

The mean planes of the nitro and methylamine groups are almost co-planar with the pyran ring, with dihedral angles of 4.66 (20) and 3.87 (19) °, respectively. The mean plane of six membered carbocyclic ring (C8–C10/C11-C13) makes a dihedral angle of 86.50 (14) ° with the chlorophenyl ring, which shows that they too are almost perpendicular to each other.

The six membered carbocyclic ring (C8-C10/C11-C13) of the chromene moiety adopts an envelope conformation on C11 atom which deviates by 0.302 (4) Å out of the mean plane formed by the remaining ring atoms. The amine group nitrogen atom N2 deviates by -0.2382 (25) Å from the pyran ring. The bromine atom Br1 deviates from the phenyl ring (C1–C6) by 0.0953 (4) Å. The title compound exhibits structural similarities with a related structure (Sun et al., 2012).

In the crystal, molecules are linked via C—H···O hydrogen bonds, which generate C(8) chains running parallel to the b axis (Bernstein et al.,1995); see Table 1 and Fig. 2. The crystal structure is further stabilized by C-H···π interactions (Table 1).

Related literature top

For the uses and biological importance of chromene, see: Ercole et al. (2009); Geen et al. (1996) Khan et al. (2010); Raj et al. (2010). For a related structure, see: Sun et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A solution of the 4-bromobenzaldehyde (0.18 g, 1.0 mmol), cyclic 1,3-dicarbonyl compound (1.0 mmol), NMSM (0.15 g, 1.0 mmol) and piperidine (0.2 equiv) in EtOH (2 ml) was stirred for 3.5 hrs. After the reaction was complete, as indicated by TLC, the product was filtered and washed with EtOH (2 ml) to remove excess base and other impurities. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in ethanol at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at 30% probability level. The intramolecular hydrogen bond, which generates an S(6) ring motif, is shown as a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed along the c-axis, showing C2—H2···O4ⁱ hydrogen bonds resulting in the formation of C(8) chains running parallel to the b axis [hydrogen atoms not involved in the hydrogen bonding have been omitted for clarity; symmetry code: (i) -x+3/2, y+1/2, -z+1/2].

4-(4-Bromophenyl)-2-methylamino-3-nitro-5,6,7,8-tetrahydro-4H-chromen-5-one top

Crystal data top

C₁₆H₁₅BrN₂O₄	F(000) = 768
M_r = 379.18	D_x = 1.575 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2053 reflections
a = 8.1114 (9) Å	θ = 2.2–26.0°
b = 10.8530 (13) Å	µ = 2.59 mm⁻¹
c = 18.222 (2) Å	T = 296 K
β = 94.399 (6)°	Block, colourless
V = 1599.4 (3) Å³	0.30 × 0.25 × 0.25 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3130 independent reflections
Radiation source: fine-focus sealed tube	2053 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω and ϕ scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
T_min = 0.464, T_max = 0.523	k = −12→13
12198 measured reflections	l = −19→22

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.047P)² + 0.3202P] where P = (F_o² + 2F_c²)/3
3130 reflections	(Δ/σ)_max = 0.002
218 parameters	Δρ_max = 0.41 e Å⁻³
4 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₁₆H₁₅BrN₂O₄	V = 1599.4 (3) Å³
M_r = 379.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1114 (9) Å	µ = 2.59 mm⁻¹
b = 10.8530 (13) Å	T = 296 K
c = 18.222 (2) Å	0.30 × 0.25 × 0.25 mm
β = 94.399 (6)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3130 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2053 reflections with I > 2σ(I)
T_min = 0.464, T_max = 0.523	R_int = 0.047
12198 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	4 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.41 e Å⁻³
3130 reflections	Δρ_min = −0.48 e Å⁻³
218 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)
C5	0.6240 (3)	0.6938 (2)	0.54373 (14)	0.0310 (6)
H5	0.5953	0.7167	0.4952	0.037*
C4	0.5278 (3)	0.6093 (3)	0.57717 (15)	0.0359 (7)
H4	0.4339	0.5763	0.5520	0.043*
C3	0.5733 (4)	0.5744 (3)	0.64890 (16)	0.0394 (7)
C2	0.7093 (3)	0.6247 (3)	0.68770 (15)	0.0386 (7)
H2	0.7379	0.6011	0.7361	0.046*
C1	0.8019 (3)	0.7104 (3)	0.65351 (14)	0.0359 (7)
H1	0.8930	0.7458	0.6796	0.043*
C6	0.7628 (3)	0.7455 (2)	0.58089 (13)	0.0279 (6)
C7	0.8703 (3)	0.8371 (2)	0.54267 (14)	0.0297 (6)
H7	0.9625	0.8614	0.5776	0.036*
C8	0.9402 (3)	0.7776 (2)	0.47729 (14)	0.0305 (6)
C9	1.0663 (3)	0.6799 (3)	0.49073 (17)	0.0384 (7)
C10	1.1286 (4)	0.6155 (3)	0.42605 (18)	0.0543 (9)
H10A	1.2327	0.6526	0.4151	0.065*	0.791 (7)
H10B	1.1504	0.5300	0.4391	0.065*	0.791 (7)
H10C	1.0740	0.5360	0.4218	0.065*	0.208 (7)
H10D	1.2456	0.5997	0.4374	0.065*	0.208 (7)
C11	1.0137 (6)	0.6194 (4)	0.3590 (2)	0.0529 (13)	0.791 (7)
H11A	0.9204	0.5658	0.3657	0.063*	0.791 (7)
H11B	1.0699	0.5882	0.3177	0.063*	0.791 (7)
C11'	1.1058 (18)	0.6734 (16)	0.3518 (6)	0.0529 (13)	0.208 (7)
H11C	1.1024	0.6091	0.3147	0.063*	0.208 (7)
H11D	1.2005	0.7254	0.3445	0.063*	0.208 (7)
C12	0.9494 (4)	0.7503 (3)	0.34074 (15)	0.0441 (8)
H12A	1.0366	0.7993	0.3216	0.053*	0.791 (7)
H12B	0.8578	0.7463	0.3034	0.053*	0.791 (7)
H12C	0.9658	0.8145	0.3050	0.053*	0.208 (7)
H12D	0.8621	0.6967	0.3201	0.053*	0.208 (7)
C13	0.8943 (3)	0.8086 (2)	0.40842 (15)	0.0331 (6)
C14	0.7371 (3)	0.9798 (2)	0.44461 (15)	0.0314 (6)
C15	0.7778 (3)	0.9516 (2)	0.51749 (14)	0.0296 (6)
C16	0.6219 (5)	1.1042 (4)	0.33983 (17)	0.0643 (10)
H16A	0.7247	1.1215	0.3191	0.096*
H16B	0.5510	1.1749	0.3342	0.096*
H16C	0.5694	1.0351	0.3149	0.096*
N1	0.7303 (3)	1.0296 (2)	0.57208 (14)	0.0391 (6)
N2	0.6532 (3)	1.0757 (2)	0.41753 (13)	0.0413 (6)
O1	0.7851 (2)	0.90458 (17)	0.39070 (10)	0.0401 (5)
O2	1.1199 (2)	0.6558 (2)	0.55357 (12)	0.0550 (6)
O3	0.6431 (3)	1.12423 (18)	0.55655 (11)	0.0497 (6)
O4	0.7744 (3)	1.0045 (2)	0.63710 (12)	0.0555 (6)
Br1	0.44896 (5)	0.45158 (4)	0.69353 (2)	0.0806 (2)
H2A	0.616 (4)	1.124 (2)	0.4528 (13)	0.058 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C5	0.0327 (15)	0.0365 (16)	0.0231 (14)	0.0076 (13)	−0.0023 (11)	0.0015 (12)
C4	0.0264 (15)	0.0419 (17)	0.0391 (18)	0.0027 (13)	−0.0004 (12)	−0.0038 (14)
C3	0.0394 (17)	0.0393 (17)	0.0411 (18)	0.0045 (14)	0.0135 (14)	0.0076 (14)
C2	0.0438 (18)	0.0467 (18)	0.0254 (15)	0.0066 (15)	0.0031 (13)	0.0056 (13)
C1	0.0355 (16)	0.0449 (17)	0.0265 (16)	0.0022 (14)	−0.0034 (12)	−0.0029 (13)
C6	0.0324 (15)	0.0278 (14)	0.0235 (14)	0.0050 (12)	0.0017 (11)	−0.0006 (11)
C7	0.0284 (14)	0.0322 (15)	0.0276 (15)	−0.0010 (12)	−0.0036 (11)	−0.0012 (12)
C8	0.0284 (14)	0.0301 (15)	0.0335 (16)	0.0001 (12)	0.0044 (12)	0.0002 (12)
C9	0.0311 (15)	0.0361 (17)	0.049 (2)	0.0002 (13)	0.0076 (14)	0.0054 (15)
C10	0.058 (2)	0.046 (2)	0.060 (2)	0.0154 (17)	0.0153 (18)	−0.0003 (17)
C11	0.051 (3)	0.053 (3)	0.054 (2)	0.014 (2)	0.004 (2)	−0.015 (2)
C11'	0.051 (3)	0.053 (3)	0.054 (2)	0.014 (2)	0.004 (2)	−0.015 (2)
C12	0.0520 (19)	0.0428 (18)	0.0384 (18)	0.0071 (15)	0.0094 (14)	−0.0051 (14)
C13	0.0334 (15)	0.0300 (15)	0.0363 (17)	0.0019 (13)	0.0063 (12)	−0.0008 (13)
C14	0.0324 (15)	0.0282 (15)	0.0344 (17)	0.0013 (13)	0.0069 (12)	0.0002 (13)
C15	0.0364 (15)	0.0252 (14)	0.0275 (16)	−0.0003 (12)	0.0042 (12)	−0.0021 (12)
C16	0.082 (3)	0.073 (2)	0.038 (2)	0.035 (2)	0.0092 (17)	0.0189 (18)
N1	0.0488 (15)	0.0331 (15)	0.0356 (16)	−0.0028 (12)	0.0041 (12)	−0.0048 (12)
N2	0.0505 (15)	0.0375 (15)	0.0365 (15)	0.0126 (12)	0.0082 (12)	0.0085 (12)
O1	0.0508 (12)	0.0419 (11)	0.0278 (10)	0.0177 (10)	0.0041 (9)	0.0000 (9)
O2	0.0472 (13)	0.0663 (15)	0.0507 (15)	0.0186 (11)	−0.0005 (11)	0.0140 (12)
O3	0.0660 (15)	0.0338 (12)	0.0497 (13)	0.0142 (11)	0.0072 (11)	−0.0046 (10)
O4	0.0869 (17)	0.0503 (13)	0.0282 (13)	0.0066 (12)	−0.0027 (11)	−0.0077 (10)
Br1	0.0731 (3)	0.0910 (4)	0.0789 (3)	−0.0277 (2)	0.0142 (2)	0.0337 (2)

Geometric parameters (Å, º) top

C5—C4	1.376 (4)	C10—H10D	0.9700
C5—C6	1.387 (3)	C11—C12	1.541 (5)
C5—H5	0.9300	C11—H11A	0.9700
C4—C3	1.384 (4)	C11—H11B	0.9700
C4—H4	0.9300	C11'—C12	1.519 (9)
C3—C2	1.376 (4)	C11'—H11C	0.9700
C3—Br1	1.893 (3)	C11'—H11D	0.9700
C2—C1	1.375 (4)	C12—C13	1.485 (4)
C2—H2	0.9300	C12—H12A	0.9700
C1—C6	1.390 (3)	C12—H12B	0.9700
C1—H1	0.9300	C12—H12C	0.9700
C6—C7	1.526 (4)	C12—H12D	0.9700
C7—C8	1.504 (4)	C13—O1	1.389 (3)
C7—C15	1.504 (4)	C14—N2	1.318 (3)
C7—H7	0.9800	C14—O1	1.357 (3)
C8—C13	1.325 (4)	C14—C15	1.378 (4)
C8—C9	1.480 (4)	C15—N1	1.383 (3)
C9—O2	1.222 (3)	C16—N2	1.452 (4)
C9—C10	1.492 (4)	C16—H16A	0.9600
C10—C11	1.480 (5)	C16—H16B	0.9600
C10—C11'	1.491 (9)	C16—H16C	0.9600
C10—H10A	0.9700	N1—O4	1.241 (3)
C10—H10B	0.9700	N1—O3	1.267 (3)
C10—H10C	0.9700	N2—H2A	0.897 (10)

C4—C5—C6	121.3 (2)	H10C—C11—H11A	75.8
C4—C5—H5	119.3	C10—C11—H11B	109.0
C6—C5—H5	119.3	C12—C11—H11B	109.0
C5—C4—C3	118.8 (3)	H10C—C11—H11B	103.5
C5—C4—H4	120.6	H11A—C11—H11B	107.8
C3—C4—H4	120.6	C10—C11'—C12	113.3 (7)
C2—C3—C4	121.5 (3)	C10—C11'—H11C	108.9
C2—C3—Br1	119.4 (2)	C12—C11'—H11C	108.9
C4—C3—Br1	119.1 (2)	C10—C11'—H11D	108.9
C3—C2—C1	118.7 (3)	C12—C11'—H11D	108.9
C3—C2—H2	120.7	H11C—C11'—H11D	107.7
C1—C2—H2	120.7	C13—C12—C11'	115.2 (5)
C2—C1—C6	121.6 (3)	C13—C12—C11	109.4 (3)
C2—C1—H1	119.2	C13—C12—H12A	109.8
C6—C1—H1	119.2	C11'—C12—H12A	74.0
C5—C6—C1	118.2 (2)	C11—C12—H12A	109.8
C5—C6—C7	120.8 (2)	C13—C12—H12B	109.8
C1—C6—C7	121.1 (2)	C11'—C12—H12B	131.0
C8—C7—C15	108.8 (2)	C11—C12—H12B	109.8
C8—C7—C6	110.2 (2)	H12A—C12—H12B	108.2
C15—C7—C6	112.9 (2)	C13—C12—H12C	108.5
C8—C7—H7	108.3	C11'—C12—H12C	109.1
C15—C7—H7	108.3	C11—C12—H12C	138.2
C6—C7—H7	108.3	H12B—C12—H12C	72.4
C13—C8—C9	118.7 (2)	C13—C12—H12D	108.7
C13—C8—C7	123.0 (2)	C11'—C12—H12D	107.4
C9—C8—C7	118.3 (2)	C11—C12—H12D	75.9
O2—C9—C8	120.0 (3)	H12A—C12—H12D	136.0
O2—C9—C10	121.5 (3)	H12C—C12—H12D	107.6
C8—C9—C10	118.5 (3)	C8—C13—O1	122.6 (2)
C11—C10—C9	114.1 (3)	C8—C13—C12	126.7 (3)
C11'—C10—C9	119.6 (6)	O1—C13—C12	110.7 (2)
C11—C10—H10A	108.7	N2—C14—O1	111.9 (2)
C11'—C10—H10A	71.8	N2—C14—C15	128.0 (2)
C9—C10—H10A	108.7	O1—C14—C15	120.2 (2)
C11—C10—H10B	108.7	C14—C15—N1	119.8 (2)
C11'—C10—H10B	129.3	C14—C15—C7	123.7 (2)
C9—C10—H10B	108.7	N1—C15—C7	116.5 (2)
H10A—C10—H10B	107.6	N2—C16—H16A	109.5
C11—C10—H10C	72.8	N2—C16—H16B	109.5
C11'—C10—H10C	106.1	H16A—C16—H16B	109.5
C9—C10—H10C	107.4	N2—C16—H16C	109.5
H10A—C10—H10C	138.8	H16A—C16—H16C	109.5
C11—C10—H10D	136.4	H16B—C16—H16C	109.5
C11'—C10—H10D	108.6	O4—N1—O3	120.4 (2)
C9—C10—H10D	107.5	O4—N1—C15	118.4 (2)
H10B—C10—H10D	67.9	O3—N1—C15	121.2 (2)
H10C—C10—H10D	107.1	C14—N2—C16	125.4 (3)
C10—C11—C12	112.7 (3)	C14—N2—H2A	112 (2)
C12—C11—H10C	143.2	C16—N2—H2A	122 (2)
C10—C11—H11A	109.0	C14—O1—C13	119.7 (2)
C12—C11—H11A	109.0

C6—C5—C4—C3	−1.1 (4)	C10—C11'—C12—C13	30.1 (16)
C5—C4—C3—C2	1.8 (4)	C10—C11'—C12—C11	−58.9 (8)
C5—C4—C3—Br1	−176.51 (19)	C10—C11—C12—C13	−47.2 (4)
C4—C3—C2—C1	−0.7 (4)	C10—C11—C12—C11'	59.3 (8)
Br1—C3—C2—C1	177.6 (2)	C9—C8—C13—O1	−175.7 (2)
C3—C2—C1—C6	−1.0 (4)	C7—C8—C13—O1	4.3 (4)
C4—C5—C6—C1	−0.6 (4)	C9—C8—C13—C12	3.7 (4)
C4—C5—C6—C7	178.8 (2)	C7—C8—C13—C12	−176.3 (3)
C2—C1—C6—C5	1.7 (4)	C11'—C12—C13—C8	−17.8 (9)
C2—C1—C6—C7	−177.7 (2)	C11—C12—C13—C8	21.6 (4)
C5—C6—C7—C8	−60.6 (3)	C11'—C12—C13—O1	161.7 (8)
C1—C6—C7—C8	118.7 (3)	C11—C12—C13—O1	−158.9 (3)
C5—C6—C7—C15	61.2 (3)	N2—C14—C15—N1	−0.6 (4)
C1—C6—C7—C15	−119.4 (3)	O1—C14—C15—N1	179.2 (2)
C15—C7—C8—C13	−13.3 (3)	N2—C14—C15—C7	178.1 (3)
C6—C7—C8—C13	110.9 (3)	O1—C14—C15—C7	−2.1 (4)
C15—C7—C8—C9	166.7 (2)	C8—C7—C15—C14	12.3 (3)
C6—C7—C8—C9	−69.1 (3)	C6—C7—C15—C14	−110.3 (3)
C13—C8—C9—O2	174.6 (3)	C8—C7—C15—N1	−168.9 (2)
C7—C8—C9—O2	−5.4 (4)	C6—C7—C15—N1	68.4 (3)
C13—C8—C9—C10	−3.6 (4)	C14—C15—N1—O4	−177.1 (2)
C7—C8—C9—C10	176.4 (2)	C7—C15—N1—O4	4.1 (4)
O2—C9—C10—C11	158.4 (3)	C14—C15—N1—O3	3.3 (4)
C8—C9—C10—C11	−23.5 (4)	C7—C15—N1—O3	−175.6 (2)
O2—C9—C10—C11'	−159.3 (9)	O1—C14—N2—C16	−3.4 (4)
C8—C9—C10—C11'	18.8 (9)	C15—C14—N2—C16	176.4 (3)
C11'—C10—C11—C12	−58.5 (7)	N2—C14—O1—C13	170.9 (2)
C9—C10—C11—C12	49.3 (5)	C15—C14—O1—C13	−8.9 (4)
C11—C10—C11'—C12	60.3 (9)	C8—C13—O1—C14	8.0 (4)
C9—C10—C11'—C12	−31.7 (17)	C12—C13—O1—C14	−171.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the pyran ring (C7/C8/C13/O1/C14/C15).

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.90 (2)	1.89 (2)	2.595 (3)	134 (2)
C2—H2···O4ⁱ	0.93	2.55	3.442 (4)	162
C10—H10B···Cg1ⁱⁱ	0.97	2.77	3.527 (3)	136
C16—H16B···Cg1ⁱⁱⁱ	0.96	2.73	3.606 (4)	153

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrN₂O₄
M_r	379.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.1114 (9), 10.8530 (13), 18.222 (2)
β (°)	94.399 (6)
V (Å³)	1599.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.59
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.464, 0.523
No. of measured, independent and observed [I > 2σ(I)] reflections	12198, 3130, 2053
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.04
No. of reflections	3130
No. of parameters	218
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.48

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the pyran ring (C7/C8/C13/O1/C14/C15).

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.90 (2)	1.89 (2)	2.595 (3)	134 (2)
C2—H2···O4ⁱ	0.93	2.55	3.442 (4)	162
C10—H10B···Cg1ⁱⁱ	0.97	2.77	3.527 (3)	136
C16—H16B···Cg1ⁱⁱⁱ	0.96	2.73	3.606 (4)	153

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

Acknowledgements

PN and KS thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT Madras, Chennai, India, for the X-ray intensity data collection.

References

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Volume 69| Part 6| June 2013| Pages o931-o932

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