7,7-Dimethyl-2-methyl-amino-4-(4-methyl-phenyl)-3-nitro-7,8-di-hydro-4H-chromen-5(6H)-one.

In the title compound, C19H22N2O4, the six-membered cyclo-hexenone ring of the chromene unit adopts an envelope conformation, with the dimethyl-substituted C atom as the flap, while the pyran ring has a boat conformation. These two mean planes are inclined to one another by 6.65 (13)°·The benzene ring is normal to the 4H-chromene moiety mean plane, making a dihedral angle of 89.18 (5)°. The methyl-amine and nitro groups are slightly twisted from the chromene moiety mean plane, with torsion angles C-N-C-O = 1.70 (18) and O-N-C-C = 0.15 (18)°. The mol-ecular structure is characterized by an intra-molecular N-H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, mol-ecules are linked via pairs of weak C-H⋯O hydrogen bonds, forming inversion dimers. These dimers are connected by further C-H⋯O hydrogen bonds, forming sheets lying parallel to (10-1).

Related literature

For the biological and pharmacological properties of chromenes and their derivatives, see: Zonouzi et al. (2013 ▶). For related structures, see: Narayanan et al. (2013 ▶); Inglebert et al. (2014 ▶).

Experimental

Crystal data

C19H22N2O4

M = 342.39

Monoclinic,

a = 9.4373 (5) Å

b = 15.8487 (8) Å

c = 12.1414 (6) Å

β = 105.122 (1)°

V = 1753.09 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.968, T max = 0.968

22747 measured reflections

4023 independent reflections

3290 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.129

S = 1.04

4023 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.27 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814010794/su2733sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010794/su2733Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814010794/su2733Isup3.cml

CCDC reference: 1002204

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H22N2O4	F(000) = 728
Mr = 342.39	Dx = 1.297 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4023 reflections
a = 9.4373 (5) Å	θ = 2.2–27.5°
b = 15.8487 (8) Å	µ = 0.09 mm−1
c = 12.1414 (6) Å	T = 293 K
β = 105.122 (1)°	Block, colourless
V = 1753.09 (15) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	4023 independent reflections
Radiation source: fine-focus sealed tube	3290 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω and φ scan	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
Tmin = 0.968, Tmax = 0.968	k = −20→20
22747 measured reflections	l = −15→15

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0725P)2 + 0.3328P] where P = (Fo2 + 2Fc2)/3
4023 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.27 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
C1	0.35586 (16)	0.13090 (10)	0.09850 (12)	0.0483 (3)
C2	0.26190 (17)	0.06267 (10)	0.06696 (12)	0.0482 (3)
H2	0.2468	0.0401	−0.0059	0.058*
C3	0.19010 (15)	0.02757 (8)	0.14194 (11)	0.0415 (3)
H3	0.1263	−0.0175	0.1184	0.050*
C4	0.21229 (13)	0.05885 (7)	0.25161 (10)	0.0337 (3)
C5	0.30488 (14)	0.12771 (8)	0.28302 (11)	0.0396 (3)
H5	0.3197	0.1505	0.3557	0.047*
C6	0.37535 (15)	0.16289 (9)	0.20772 (12)	0.0458 (3)
H6	0.4371	0.2089	0.2307	0.055*
C7	0.4372 (2)	0.16838 (15)	0.01843 (17)	0.0787 (6)
H7A	0.4967	0.2146	0.0554	0.118*
H7B	0.3679	0.1883	−0.0492	0.118*
H7C	0.4987	0.1261	−0.0018	0.118*
C8	0.41028 (17)	0.05680 (10)	0.74565 (12)	0.0526 (4)
H8A	0.4903	0.0313	0.8011	0.079*
H8B	0.3235	0.0552	0.7728	0.079*
H8C	0.4343	0.1143	0.7336	0.079*
C9	−0.19570 (18)	0.30022 (10)	0.45333 (15)	0.0582 (4)
H9A	−0.2572	0.2675	0.4889	0.087*
H9B	−0.2558	0.3308	0.3899	0.087*
H9C	−0.1388	0.3392	0.5077	0.087*
C10	0.00622 (16)	0.29312 (9)	0.35491 (13)	0.0492 (3)
H10A	−0.0532	0.3238	0.2913	0.074*
H10B	0.0708	0.2559	0.3287	0.074*
H10C	0.0632	0.3320	0.4094	0.074*
C11	0.13852 (13)	0.01918 (7)	0.33750 (10)	0.0339 (3)
H11	0.0773	−0.0281	0.3006	0.041*
C12	0.24902 (13)	−0.01314 (7)	0.44158 (10)	0.0343 (3)
C13	0.28241 (13)	0.02932 (8)	0.54548 (10)	0.0352 (3)
C14	0.08036 (14)	0.12100 (8)	0.47489 (10)	0.0362 (3)
C15	0.00113 (15)	0.19200 (9)	0.51285 (11)	0.0425 (3)
H15A	0.0718	0.2298	0.5609	0.051*
H15B	−0.0615	0.1699	0.5580	0.051*
C16	−0.09273 (14)	0.24144 (8)	0.41109 (12)	0.0406 (3)
C17	−0.18292 (14)	0.17886 (9)	0.32523 (12)	0.0440 (3)
H17A	−0.2584	0.1552	0.3570	0.053*
H17B	−0.2318	0.2095	0.2567	0.053*
C18	−0.09720 (13)	0.10749 (8)	0.29228 (11)	0.0388 (3)
C19	0.04223 (13)	0.08322 (8)	0.37386 (10)	0.0344 (3)
N1	0.38424 (12)	0.01069 (7)	0.63882 (9)	0.0410 (3)
H1	0.4396	−0.0320	0.6365	0.049*
N2	0.32677 (12)	−0.08485 (7)	0.42859 (9)	0.0378 (2)
O1	0.20515 (10)	0.09898 (6)	0.55876 (7)	0.0424 (2)
O2	−0.14135 (11)	0.06874 (7)	0.20344 (9)	0.0559 (3)
O3	0.42802 (11)	−0.11268 (6)	0.51012 (9)	0.0484 (3)
O4	0.29464 (12)	−0.12159 (6)	0.33498 (9)	0.0508 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0473 (7)	0.0549 (8)	0.0458 (8)	0.0037 (6)	0.0177 (6)	0.0092 (6)
C2	0.0579 (8)	0.0548 (8)	0.0333 (7)	0.0044 (7)	0.0147 (6)	−0.0007 (6)
C3	0.0481 (7)	0.0391 (7)	0.0363 (6)	−0.0009 (6)	0.0092 (5)	−0.0022 (5)
C4	0.0342 (6)	0.0340 (6)	0.0318 (6)	0.0034 (5)	0.0068 (5)	0.0018 (5)
C5	0.0397 (6)	0.0417 (7)	0.0356 (6)	−0.0020 (5)	0.0069 (5)	−0.0031 (5)
C6	0.0415 (7)	0.0446 (7)	0.0511 (8)	−0.0053 (6)	0.0116 (6)	0.0026 (6)
C7	0.0853 (13)	0.0951 (15)	0.0681 (12)	−0.0151 (11)	0.0421 (10)	0.0092 (11)
C8	0.0526 (8)	0.0620 (9)	0.0371 (7)	0.0013 (7)	0.0007 (6)	−0.0017 (6)
C9	0.0604 (9)	0.0534 (9)	0.0656 (10)	0.0194 (7)	0.0253 (8)	0.0050 (7)
C10	0.0491 (7)	0.0431 (7)	0.0560 (8)	−0.0010 (6)	0.0147 (6)	0.0081 (6)
C11	0.0356 (6)	0.0322 (6)	0.0327 (6)	−0.0009 (5)	0.0069 (5)	−0.0008 (5)
C12	0.0359 (6)	0.0323 (6)	0.0345 (6)	0.0006 (5)	0.0088 (5)	0.0033 (5)
C13	0.0361 (6)	0.0335 (6)	0.0357 (6)	−0.0007 (5)	0.0090 (5)	0.0055 (5)
C14	0.0377 (6)	0.0375 (6)	0.0335 (6)	0.0027 (5)	0.0093 (5)	0.0055 (5)
C15	0.0492 (7)	0.0432 (7)	0.0375 (7)	0.0078 (6)	0.0153 (6)	0.0012 (5)
C16	0.0398 (6)	0.0398 (7)	0.0445 (7)	0.0063 (5)	0.0150 (6)	0.0048 (5)
C17	0.0321 (6)	0.0491 (7)	0.0505 (8)	0.0038 (5)	0.0102 (5)	0.0068 (6)
C18	0.0337 (6)	0.0440 (7)	0.0382 (7)	−0.0030 (5)	0.0085 (5)	0.0040 (5)
C19	0.0336 (6)	0.0360 (6)	0.0338 (6)	0.0007 (5)	0.0090 (5)	0.0030 (5)
N1	0.0419 (6)	0.0427 (6)	0.0350 (6)	0.0037 (5)	0.0041 (4)	0.0041 (4)
N2	0.0374 (5)	0.0354 (5)	0.0412 (6)	0.0004 (4)	0.0112 (4)	0.0036 (4)
O1	0.0480 (5)	0.0411 (5)	0.0337 (5)	0.0089 (4)	0.0027 (4)	−0.0012 (4)
O2	0.0455 (5)	0.0683 (7)	0.0460 (6)	0.0028 (5)	−0.0020 (4)	−0.0096 (5)
O3	0.0470 (5)	0.0467 (5)	0.0485 (6)	0.0123 (4)	0.0070 (4)	0.0074 (4)
O4	0.0571 (6)	0.0454 (5)	0.0479 (6)	0.0059 (4)	0.0099 (5)	−0.0100 (4)

C1—C6	1.386 (2)	C10—H10B	0.9600
C1—C2	1.387 (2)	C10—H10C	0.9600
C1—C7	1.509 (2)	C11—C12	1.5030 (17)
C2—C3	1.3854 (19)	C11—C19	1.5034 (17)
C2—H2	0.9300	C11—H11	0.9800
C3—C4	1.3846 (17)	C12—N2	1.3840 (16)
C3—H3	0.9300	C12—C13	1.3915 (17)
C4—C5	1.3879 (18)	C13—N1	1.3141 (16)
C4—C11	1.5318 (16)	C13—O1	1.3557 (15)
C5—C6	1.3806 (19)	C14—C19	1.3275 (17)
C5—H5	0.9300	C14—O1	1.3857 (15)
C6—H6	0.9300	C14—C15	1.4891 (18)
C7—H7A	0.9600	C15—C16	1.5342 (18)
C7—H7B	0.9600	C15—H15A	0.9700
C7—H7C	0.9600	C15—H15B	0.9700
C8—N1	1.4528 (18)	C16—C17	1.527 (2)
C8—H8A	0.9600	C17—C18	1.5043 (19)
C8—H8B	0.9600	C17—H17A	0.9700
C8—H8C	0.9600	C17—H17B	0.9700
C9—C16	1.5281 (19)	C18—O2	1.2165 (16)
C9—H9A	0.9600	C18—C19	1.4767 (17)
C9—H9B	0.9600	N1—H1	0.8600
C9—H9C	0.9600	N2—O4	1.2421 (14)
C10—C16	1.5299 (19)	N2—O3	1.2626 (14)
C10—H10A	0.9600
C6—C1—C2	117.69 (13)	C19—C11—C4	109.86 (10)
C6—C1—C7	120.63 (15)	C12—C11—H11	108.7
C2—C1—C7	121.66 (15)	C19—C11—H11	108.7
C3—C2—C1	121.24 (13)	C4—C11—H11	108.7
C3—C2—H2	119.4	N2—C12—C13	119.94 (11)
C1—C2—H2	119.4	N2—C12—C11	117.14 (11)
C4—C3—C2	120.73 (13)	C13—C12—C11	122.74 (11)
C4—C3—H3	119.6	N1—C13—O1	112.05 (11)
C2—C3—H3	119.6	N1—C13—C12	127.95 (12)
C3—C4—C5	118.18 (12)	O1—C13—C12	120.00 (11)
C3—C4—C11	121.74 (11)	C19—C14—O1	122.61 (11)
C5—C4—C11	120.07 (11)	C19—C14—C15	126.15 (12)
C6—C5—C4	120.87 (12)	O1—C14—C15	111.22 (11)
C6—C5—H5	119.6	C14—C15—C16	111.57 (11)
C4—C5—H5	119.6	C14—C15—H15A	109.3
C5—C6—C1	121.27 (13)	C16—C15—H15A	109.3
C5—C6—H6	119.4	C14—C15—H15B	109.3
C1—C6—H6	119.4	C16—C15—H15B	109.3
C1—C7—H7A	109.5	H15A—C15—H15B	108.0
C1—C7—H7B	109.5	C17—C16—C9	109.58 (12)
H7A—C7—H7B	109.5	C17—C16—C10	109.86 (11)
C1—C7—H7C	109.5	C9—C16—C10	109.80 (12)
H7A—C7—H7C	109.5	C17—C16—C15	108.66 (11)
H7B—C7—H7C	109.5	C9—C16—C15	108.98 (11)
N1—C8—H8A	109.5	C10—C16—C15	109.95 (11)
N1—C8—H8B	109.5	C18—C17—C16	115.30 (10)
H8A—C8—H8B	109.5	C18—C17—H17A	108.5
N1—C8—H8C	109.5	C16—C17—H17A	108.5
H8A—C8—H8C	109.5	C18—C17—H17B	108.5
H8B—C8—H8C	109.5	C16—C17—H17B	108.5
C16—C9—H9A	109.5	H17A—C17—H17B	107.5
C16—C9—H9B	109.5	O2—C18—C19	120.16 (12)
H9A—C9—H9B	109.5	O2—C18—C17	122.13 (12)
C16—C9—H9C	109.5	C19—C18—C17	117.67 (11)
H9A—C9—H9C	109.5	C14—C19—C18	118.79 (12)
H9B—C9—H9C	109.5	C14—C19—C11	122.48 (11)
C16—C10—H10A	109.5	C18—C19—C11	118.69 (11)
C16—C10—H10B	109.5	C13—N1—C8	124.91 (12)
H10A—C10—H10B	109.5	C13—N1—H1	117.5
C16—C10—H10C	109.5	C8—N1—H1	117.5
H10A—C10—H10C	109.5	O4—N2—O3	120.52 (11)
H10B—C10—H10C	109.5	O4—N2—C12	118.63 (11)
C12—C11—C19	108.85 (10)	O3—N2—C12	120.85 (11)
C12—C11—C4	111.92 (10)	C13—O1—C14	119.87 (10)
C6—C1—C2—C3	−0.1 (2)	C9—C16—C17—C18	−169.54 (12)
C7—C1—C2—C3	178.62 (16)	C10—C16—C17—C18	69.75 (15)
C1—C2—C3—C4	−1.1 (2)	C15—C16—C17—C18	−50.56 (15)
C2—C3—C4—C5	1.85 (19)	C16—C17—C18—O2	−157.41 (13)
C2—C3—C4—C11	−177.78 (12)	C16—C17—C18—C19	24.66 (17)
C3—C4—C5—C6	−1.36 (19)	O1—C14—C19—C18	176.46 (11)
C11—C4—C5—C6	178.27 (12)	C15—C14—C19—C18	−5.1 (2)
C4—C5—C6—C1	0.2 (2)	O1—C14—C19—C11	−6.08 (19)
C2—C1—C6—C5	0.6 (2)	C15—C14—C19—C11	172.31 (12)
C7—C1—C6—C5	−178.14 (16)	O2—C18—C19—C14	−173.35 (13)
C3—C4—C11—C12	119.44 (13)	C17—C18—C19—C14	4.61 (18)
C5—C4—C11—C12	−60.18 (15)	O2—C18—C19—C11	9.09 (18)
C3—C4—C11—C19	−119.52 (12)	C17—C18—C19—C11	−172.94 (11)
C5—C4—C11—C19	60.86 (14)	C12—C11—C19—C14	18.29 (16)
C19—C11—C12—N2	166.69 (10)	C4—C11—C19—C14	−104.58 (13)
C4—C11—C12—N2	−71.68 (13)	C12—C11—C19—C18	−164.25 (10)
C19—C11—C12—C13	−18.20 (16)	C4—C11—C19—C18	72.88 (13)
C4—C11—C12—C13	103.42 (13)	O1—C13—N1—C8	1.70 (18)
N2—C12—C13—N1	0.7 (2)	C12—C13—N1—C8	−178.21 (13)
C11—C12—C13—N1	−174.26 (12)	C13—C12—N2—O4	179.94 (11)
N2—C12—C13—O1	−179.19 (11)	C11—C12—N2—O4	−4.82 (16)
C11—C12—C13—O1	5.84 (18)	C13—C12—N2—O3	0.15 (18)
C19—C14—C15—C16	−23.05 (19)	C11—C12—N2—O3	175.40 (11)
O1—C14—C15—C16	155.49 (11)	N1—C13—O1—C14	−170.87 (11)
C14—C15—C16—C17	48.46 (15)	C12—C13—O1—C14	9.05 (17)
C14—C15—C16—C9	167.81 (12)	C19—C14—O1—C13	−9.14 (18)
C14—C15—C16—C10	−71.80 (15)	C15—C14—O1—C13	172.26 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	1.98	2.6024 (15)	129
C5—H5···O3i	0.93	2.58	3.0685 (17)	113
C10—H10A···O4ii	0.96	2.54	3.4335 (19)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.86	1.98	2.6024 (15)	129
C5—H5⋯O3i	0.93	2.58	3.0685 (17)	113
C10—H10A⋯O4ii	0.96	2.54	3.4335 (19)	154

Symmetry codes: (i) ; (ii) .