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

The title compound, C16H15ClN2O4, contains a chiral centre and crystallizes as a racemate. The methyl-ene group β-positioned to the carbonyl group is partially (21%) disordered. It flips to the opposite sides of the corresponding six-membered carbocycle by -0.304 (3) and 0.197 (11) Å, producing alternative envelope conformations. The planes of the pyran and chloro-phenyl rings form a dihedral angle of 86.25 (9)°. The mol-ecular structure is characterized by an intra-molecular N-H⋯O inter-action, which generates an S(6) ring motif. The corresponding amino N atom deviates from the plane of the pyran ring by 0.1634 (19) Å. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds, forming C(8) chains running parallel to the b-axis direction. The crystal structure also features C-H⋯π inter-actions.

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 related structures, see: Sun et al., (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C16H15ClN2O4

M = 334.75

Monoclinic,

a = 8.0285 (4) Å

b = 10.8460 (5) Å

c = 18.2337 (9) Å

β = 94.067 (2)°

V = 1583.74 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.35 × 0.30 × 0.30 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.912, T max = 0.924

11848 measured reflections

2786 independent reflections

2208 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.119

S = 1.09

2786 reflections

218 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.28 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813014530/ld2104sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014530/ld2104Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813014530/ld2104Isup3.cml

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

C16H15ClN2O4	F(000) = 696
Mr = 334.75	Dx = 1.404 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2208 reflections
a = 8.0285 (4) Å	θ = 2.2–25.0°
b = 10.8460 (5) Å	µ = 0.26 mm−1
c = 18.2337 (9) Å	T = 296 K
β = 94.067 (2)°	Block, colourless
V = 1583.74 (13) Å3	0.35 × 0.30 × 0.30 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	2786 independent reflections
Radiation source: fine-focus sealed tube	2208 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and φ scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→8
Tmin = 0.912, Tmax = 0.924	k = −12→12
11848 measured reflections	l = −15→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.9511P] where P = (Fo2 + 2Fc2)/3
2786 reflections	(Δ/σ)max = 0.002
218 parameters	Δρmax = 0.32 e Å−3
4 restraints	Δρmin = −0.28 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)
C1	0.8013 (3)	0.7871 (2)	0.15451 (11)	0.0393 (5)
H1	0.8934	0.7510	0.1798	0.047*
C2	0.7070 (3)	0.8723 (2)	0.19018 (12)	0.0440 (5)
H2	0.7358	0.8944	0.2387	0.053*
C3	0.5699 (3)	0.9234 (2)	0.15224 (13)	0.0443 (5)
C4	0.5244 (3)	0.8923 (2)	0.08060 (13)	0.0426 (5)
H4	0.4302	0.9271	0.0561	0.051*
C5	0.6215 (2)	0.80814 (19)	0.04556 (11)	0.0359 (5)
H5	0.5927	0.7870	−0.0031	0.043*
C6	0.7614 (2)	0.75474 (18)	0.08203 (11)	0.0321 (4)
C7	0.8702 (2)	0.66430 (18)	0.04219 (11)	0.0333 (5)
H7	0.9648	0.6402	0.0761	0.040*
C8	0.9376 (2)	0.72565 (18)	−0.02368 (11)	0.0340 (5)
C9	1.0653 (3)	0.8231 (2)	−0.01071 (13)	0.0408 (5)
C10	1.1262 (3)	0.8872 (2)	−0.07623 (15)	0.0568 (7)
H10A	1.1514	0.9722	−0.0631	0.068*	0.787 (5)
H10B	1.2293	0.8485	−0.0888	0.068*	0.787 (5)
H10C	1.0732	0.9676	−0.0794	0.068*	0.213 (5)
H10D	1.2450	0.9012	−0.0664	0.068*	0.213 (5)
C11	1.0072 (4)	0.8859 (3)	−0.14166 (18)	0.0539 (9)	0.787 (5)
H11A	1.0619	0.9181	−0.1834	0.065*	0.787 (5)
H11B	0.9140	0.9397	−0.1331	0.065*	0.787 (5)
C11'	1.1015 (14)	0.8288 (11)	−0.1501 (5)	0.0539 (9)	0.213 (5)
H11C	1.1949	0.7744	−0.1572	0.065*	0.213 (5)
H11D	1.1009	0.8925	−0.1874	0.065*	0.213 (5)
C12	0.9406 (3)	0.7556 (2)	−0.16027 (13)	0.0488 (6)
H12A	0.8457	0.7608	−0.1962	0.059*	0.787 (5)
H12B	1.0268	0.7070	−0.1813	0.059*	0.787 (5)
H12C	0.9528	0.6925	−0.1972	0.059*	0.213 (5)
H12D	0.8519	0.8105	−0.1787	0.059*	0.213 (5)
C13	0.8893 (3)	0.69552 (19)	−0.09213 (11)	0.0360 (5)
C14	0.7355 (2)	0.52214 (18)	−0.05564 (11)	0.0344 (5)
C15	0.7772 (2)	0.54932 (18)	0.01722 (11)	0.0329 (5)
C16	0.6240 (4)	0.3970 (3)	−0.15987 (14)	0.0699 (9)
H16A	0.5475	0.4562	−0.1823	0.105*
H16B	0.5771	0.3158	−0.1655	0.105*
H16C	0.7275	0.4004	−0.1831	0.105*
N1	0.7340 (2)	0.46946 (16)	0.07175 (10)	0.0408 (4)
N2	0.6539 (2)	0.42483 (17)	−0.08263 (10)	0.0442 (5)
O1	0.77966 (19)	0.59923 (14)	−0.10937 (8)	0.0436 (4)
O2	1.1201 (2)	0.84650 (17)	0.05139 (10)	0.0574 (5)
O3	0.6480 (2)	0.37405 (14)	0.05646 (9)	0.0529 (4)
O4	0.7809 (3)	0.49375 (16)	0.13643 (9)	0.0593 (5)
Cl1	0.45353 (11)	1.03329 (9)	0.19602 (5)	0.0864 (3)
H2A	0.621 (3)	0.377 (2)	−0.0458 (10)	0.058 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0421 (12)	0.0421 (12)	0.0334 (11)	−0.0032 (10)	0.0014 (9)	0.0005 (9)
C2	0.0523 (13)	0.0468 (13)	0.0341 (12)	−0.0107 (11)	0.0099 (10)	−0.0078 (10)
C3	0.0439 (12)	0.0403 (12)	0.0510 (14)	−0.0058 (10)	0.0186 (10)	−0.0095 (11)
C4	0.0342 (11)	0.0407 (12)	0.0533 (14)	−0.0023 (9)	0.0048 (10)	0.0005 (10)
C5	0.0362 (11)	0.0359 (11)	0.0354 (11)	−0.0074 (9)	0.0023 (8)	−0.0038 (9)
C6	0.0334 (10)	0.0292 (10)	0.0342 (11)	−0.0072 (8)	0.0056 (8)	−0.0008 (8)
C7	0.0329 (10)	0.0325 (11)	0.0342 (11)	−0.0016 (8)	−0.0002 (8)	0.0004 (9)
C8	0.0325 (10)	0.0301 (11)	0.0401 (12)	−0.0018 (8)	0.0065 (8)	−0.0025 (9)
C9	0.0336 (11)	0.0371 (12)	0.0520 (14)	−0.0031 (9)	0.0066 (10)	−0.0091 (10)
C10	0.0599 (15)	0.0415 (14)	0.0707 (17)	−0.0169 (12)	0.0173 (13)	−0.0015 (12)
C11	0.062 (2)	0.0432 (19)	0.0571 (19)	−0.0125 (14)	0.0095 (16)	0.0095 (15)
C11'	0.062 (2)	0.0432 (19)	0.0571 (19)	−0.0125 (14)	0.0095 (16)	0.0095 (15)
C12	0.0615 (15)	0.0446 (13)	0.0417 (13)	−0.0119 (11)	0.0136 (11)	0.0021 (10)
C13	0.0379 (11)	0.0303 (11)	0.0405 (12)	−0.0044 (9)	0.0084 (9)	−0.0011 (9)
C14	0.0345 (10)	0.0297 (10)	0.0399 (12)	−0.0027 (8)	0.0081 (8)	−0.0001 (9)
C15	0.0360 (10)	0.0271 (10)	0.0358 (11)	−0.0005 (8)	0.0044 (8)	0.0014 (8)
C16	0.087 (2)	0.076 (2)	0.0483 (16)	−0.0372 (16)	0.0119 (14)	−0.0187 (14)
N1	0.0514 (11)	0.0311 (10)	0.0404 (11)	0.0013 (8)	0.0063 (8)	0.0047 (8)
N2	0.0542 (11)	0.0378 (11)	0.0416 (11)	−0.0144 (9)	0.0102 (9)	−0.0070 (9)
O1	0.0555 (9)	0.0415 (9)	0.0341 (8)	−0.0178 (7)	0.0051 (7)	−0.0012 (7)
O2	0.0482 (10)	0.0634 (11)	0.0606 (12)	−0.0179 (8)	0.0035 (8)	−0.0148 (9)
O3	0.0695 (11)	0.0331 (9)	0.0572 (11)	−0.0129 (8)	0.0109 (8)	0.0050 (7)
O4	0.0923 (14)	0.0494 (10)	0.0353 (10)	−0.0065 (9)	−0.0008 (9)	0.0095 (8)
Cl1	0.0797 (5)	0.0901 (6)	0.0916 (6)	0.0240 (4)	0.0224 (4)	−0.0350 (5)

C1—C6	1.383 (3)	C10—H10D	0.9700
C1—C2	1.386 (3)	C11—C12	1.540 (4)
C1—H1	0.9300	C11—H11A	0.9700
C2—C3	1.375 (3)	C11—H11B	0.9700
C2—H2	0.9300	C11'—C12	1.516 (8)
C3—C4	1.373 (3)	C11'—H11C	0.9700
C3—Cl1	1.742 (2)	C11'—H11D	0.9700
C4—C5	1.386 (3)	C12—C13	1.487 (3)
C4—H4	0.9300	C12—H12A	0.9700
C5—C6	1.390 (3)	C12—H12B	0.9700
C5—H5	0.9300	C12—H12C	0.9700
C6—C7	1.531 (3)	C12—H12D	0.9700
C7—C8	1.507 (3)	C13—O1	1.387 (2)
C7—C15	1.507 (3)	C14—N2	1.319 (3)
C7—H7	0.9800	C14—O1	1.354 (2)
C8—C13	1.321 (3)	C14—C15	1.379 (3)
C8—C9	1.480 (3)	C15—N1	1.381 (3)
C9—O2	1.212 (3)	C16—N2	1.444 (3)
C9—C10	1.494 (3)	C16—H16A	0.9600
C10—C11	1.475 (4)	C16—H16B	0.9600
C10—C11'	1.489 (8)	C16—H16C	0.9600
C10—H10A	0.9700	N1—O4	1.241 (2)
C10—H10B	0.9700	N1—O3	1.264 (2)
C10—H10C	0.9700	N2—H2A	0.901 (10)
C6—C1—C2	121.4 (2)	C12—C11—H11A	109.1
C6—C1—H1	119.3	C10—C11—H11B	109.1
C2—C1—H1	119.3	C12—C11—H11B	109.1
C3—C2—C1	118.5 (2)	H11A—C11—H11B	107.8
C3—C2—H2	120.7	C10—C11'—C12	113.0 (6)
C1—C2—H2	120.7	C10—C11'—H11C	109.0
C4—C3—C2	122.0 (2)	C12—C11'—H11C	109.0
C4—C3—Cl1	119.25 (19)	C10—C11'—H11D	109.0
C2—C3—Cl1	118.77 (18)	C12—C11'—H11D	109.0
C3—C4—C5	118.7 (2)	H11C—C11'—H11D	107.8
C3—C4—H4	120.7	C13—C12—C11'	114.3 (4)
C5—C4—H4	120.7	C13—C12—C11	109.3 (2)
C4—C5—C6	121.05 (19)	C13—C12—H12A	109.8
C4—C5—H5	119.5	C11'—C12—H12A	132.3
C6—C5—H5	119.5	C11—C12—H12A	109.8
C1—C6—C5	118.42 (19)	C13—C12—H12B	109.8
C1—C6—C7	120.98 (18)	C11'—C12—H12B	72.9
C5—C6—C7	120.58 (17)	C11—C12—H12B	109.8
C8—C7—C15	108.83 (16)	H12A—C12—H12B	108.3
C8—C7—C6	110.16 (16)	C13—C12—H12C	108.6
C15—C7—C6	112.73 (16)	C11'—C12—H12C	109.1
C8—C7—H7	108.3	C11—C12—H12C	138.6
C15—C7—H7	108.3	H12A—C12—H12C	71.7
C6—C7—H7	108.3	C13—C12—H12D	108.6
C13—C8—C9	118.77 (19)	C11'—C12—H12D	108.6
C13—C8—C7	123.07 (18)	C11—C12—H12D	75.4
C9—C8—C7	118.15 (18)	H12B—C12—H12D	136.4
O2—C9—C8	120.0 (2)	H12C—C12—H12D	107.5
O2—C9—C10	122.1 (2)	C8—C13—O1	122.63 (18)
C8—C9—C10	117.8 (2)	C8—C13—C12	126.9 (2)
C11—C10—C9	114.4 (2)	O1—C13—C12	110.45 (18)
C11'—C10—C9	119.7 (4)	N2—C14—O1	111.88 (18)
C11—C10—H10A	108.7	N2—C14—C15	127.66 (19)
C11'—C10—H10A	129.7	O1—C14—C15	120.45 (18)
C9—C10—H10A	108.7	C14—C15—N1	120.21 (18)
C11—C10—H10B	108.7	C14—C15—C7	123.32 (18)
C11'—C10—H10B	70.3	N1—C15—C7	116.47 (17)
C9—C10—H10B	108.7	N2—C16—H16A	109.5
H10A—C10—H10B	107.6	N2—C16—H16B	109.5
C11—C10—H10C	72.8	H16A—C16—H16B	109.5
C11'—C10—H10C	107.4	N2—C16—H16C	109.5
C9—C10—H10C	107.4	H16A—C16—H16C	109.5
H10B—C10—H10C	138.8	H16B—C16—H16C	109.5
C11—C10—H10D	136.3	O4—N1—O3	120.52 (18)
C11'—C10—H10D	107.4	O4—N1—C15	118.43 (18)
C9—C10—H10D	107.4	O3—N1—C15	121.05 (18)
H10A—C10—H10D	67.7	C14—N2—C16	125.1 (2)
H10C—C10—H10D	106.9	C14—N2—H2A	110.2 (17)
C10—C11—C12	112.5 (2)	C16—N2—H2A	124.7 (17)
C10—C11—H11A	109.1	C14—O1—C13	119.69 (16)
C6—C1—C2—C3	0.9 (3)	C10—C11'—C12—C13	−33.1 (11)
C1—C2—C3—C4	0.1 (3)	C10—C11'—C12—C11	57.6 (6)
C1—C2—C3—Cl1	−178.49 (17)	C10—C11—C12—C13	46.9 (3)
C2—C3—C4—C5	−0.9 (3)	C10—C11—C12—C11'	−58.2 (6)
Cl1—C3—C4—C5	177.67 (16)	C9—C8—C13—O1	175.11 (18)
C3—C4—C5—C6	0.7 (3)	C7—C8—C13—O1	−4.1 (3)
C2—C1—C6—C5	−1.1 (3)	C9—C8—C13—C12	−4.8 (3)
C2—C1—C6—C7	177.64 (19)	C7—C8—C13—C12	176.0 (2)
C4—C5—C6—C1	0.3 (3)	C11'—C12—C13—C8	20.5 (7)
C4—C5—C6—C7	−178.48 (18)	C11—C12—C13—C8	−20.3 (3)
C1—C6—C7—C8	−119.8 (2)	C11'—C12—C13—O1	−159.3 (6)
C5—C6—C7—C8	58.9 (2)	C11—C12—C13—O1	159.8 (2)
C1—C6—C7—C15	118.4 (2)	N2—C14—C15—N1	0.5 (3)
C5—C6—C7—C15	−62.8 (2)	O1—C14—C15—N1	−179.05 (18)
C15—C7—C8—C13	13.3 (3)	N2—C14—C15—C7	−179.6 (2)
C6—C7—C8—C13	−110.8 (2)	O1—C14—C15—C7	0.9 (3)
C15—C7—C8—C9	−166.00 (17)	C8—C7—C15—C14	−11.7 (3)
C6—C7—C8—C9	69.9 (2)	C6—C7—C15—C14	110.8 (2)
C13—C8—C9—O2	−174.9 (2)	C8—C7—C15—N1	168.27 (17)
C7—C8—C9—O2	4.4 (3)	C6—C7—C15—N1	−69.2 (2)
C13—C8—C9—C10	3.3 (3)	C14—C15—N1—O4	176.39 (19)
C7—C8—C9—C10	−177.4 (2)	C7—C15—N1—O4	−3.6 (3)
O2—C9—C10—C11	−156.9 (3)	C14—C15—N1—O3	−3.9 (3)
C8—C9—C10—C11	24.9 (3)	C7—C15—N1—O3	176.11 (18)
O2—C9—C10—C11'	159.0 (6)	O1—C14—N2—C16	4.2 (3)
C8—C9—C10—C11'	−19.1 (7)	C15—C14—N2—C16	−175.4 (2)
C11'—C10—C11—C12	57.4 (6)	N2—C14—O1—C13	−169.49 (18)
C9—C10—C11—C12	−50.4 (4)	C15—C14—O1—C13	10.1 (3)
C11—C10—C11'—C12	−59.2 (7)	C8—C13—O1—C14	−8.7 (3)
C9—C10—C11'—C12	33.9 (11)	C12—C13—O1—C14	171.21 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.90 (2)	1.86 (2)	2.599 (2)	137 (2)
C2—H2···O4i	0.93	2.53	3.420 (3)	160
C10—H10A···Cg1ii	0.97	2.75	3.515 (2)	136
C16—H16B···Cg1iii	0.96	2.76	3.577 (3)	144

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)	1.86 (2)	2.599 (2)	137 (2)
C2—H2⋯O4i	0.93	2.53	3.420 (3)	160
C10—H10A⋯Cg1ii	0.97	2.75	3.515 (2)	136
C16—H16B⋯Cg1iii	0.96	2.76	3.577 (3)	144

Symmetry codes: (i) ; (ii) ; (iii) .