4-(4-Bromo-phen-yl)-2-methyl-amino-3-nitro-5,6,7,8-tetra-hydro-4H-chromen-5-one.

In the title compound, C16H15BrN2O4, the six-membered carbocyclic ring of the chromene moiety adopts an envelope conformation with the disordered methyl-ene C atom as the flap. The pyran ring is almost orthogonal to the chloro-phenyl 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 mol-ecular structure is stabilized by an intra-molecular N-H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, mol-ecules 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 inter-actions. The methyl-ene-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 = 379.18

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.101

S = 1.04

3130 reflections

218 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.48 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012774/su2597sup1.cif

Click here for additional data file.

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012774/su2597Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H15BrN2O4	F(000) = 768
Mr = 379.18	Dx = 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

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

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(Fo2) + (0.047P)2 + 0.3202P] where P = (Fo2 + 2Fc2)/3
3130 reflections	(Δ/σ)max = 0.002
218 parameters	Δρmax = 0.41 e Å−3
4 restraints	Δρmin = −0.48 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)*

	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)

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)

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

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) ; (ii) ; (iii) .