Crystal structure of 4-(4-meth-oxy-phen-yl)-7,7-dimethyl-2-methyl-amino-3-nitro-7,8-di-hydro-4H-chromen-5(6H)-one.

In the title compound, C19H22N2O5, the six-membered carbocyclic ring of the chromene moiety adopts an envelope conformation with the dimethyl-substituted C atom as the flap. The pyran ring has a flat-boat conformation. The meth-oxy-phenyl ring is orthogonal to the mean plane of the chromene moiety, with a dihedral angle of 89.97 (8)°. The amine N atom deviates from the chromene mean plane by 0.1897 (16) Å. The methyl-amine and the nitro group are involved in an intra-molecular N-H⋯O hydrogen bond which generates an S(6) ring motif. They are slightly twisted out of the plane of the chromene moiety with torsion angles of C-N-C-O(pyran) = 2.2 (3)° and O(nitro)-N-C-C = -5.6 (2)°. In the crystal, there are only C-H⋯π inter-actions present, forming inversion-related dimers.

Related literature

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

Experimental

Crystal data

C19H22N2O5

M = 358.39

Monoclinic,

a = 9.6793 (7) Å

b = 16.3059 (12) Å

c = 11.9205 (8) Å

β = 106.128 (2)°

V = 1807.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.10 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 = 0.972, T max = 0.981

25137 measured reflections

3429 independent reflections

2369 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.140

S = 1.04

3429 reflections

239 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.23 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/S160053681401589X/su2750sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401589X/su2750Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401589X/su2750Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681401589X/su2750fig1.tif

A view of the mol­ecular structure of the title mol­ecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

CCDC reference: 1012691

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

C19H22N2O5	F(000) = 760
Mr = 358.39	Dx = 1.317 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 3429 reflections
a = 9.6793 (7) Å	θ = 2.2–25.7°
b = 16.3059 (12) Å	µ = 0.10 mm−1
c = 11.9205 (8) Å	T = 293 K
β = 106.128 (2)°	Block, colourless
V = 1807.4 (2) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3429 independent reflections
Radiation source: fine-focus sealed tube	2369 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω and φ scan	θmax = 25.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.972, Tmax = 0.981	k = −19→19
25137 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0743P)2 + 0.445P] where P = (Fo2 + 2Fc2)/3
3429 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.23 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	0.3188 (2)	0.60966 (13)	0.57925 (17)	0.0418 (5)
C2	0.3527 (2)	0.64520 (13)	0.68892 (17)	0.0438 (5)
H2	0.4155	0.6895	0.7066	0.053*
C3	0.2913 (2)	0.61357 (12)	0.77209 (16)	0.0404 (5)
H3	0.3137	0.6376	0.8457	0.049*
C4	0.19830 (18)	0.54764 (11)	0.74909 (15)	0.0338 (4)
C5	0.1649 (2)	0.51385 (12)	0.63813 (16)	0.0397 (5)
H5	0.1009	0.4701	0.6200	0.048*
C6	0.2248 (2)	0.54378 (13)	0.55413 (17)	0.0450 (5)
H6	0.2020	0.5198	0.4805	0.054*
C7	0.1347 (2)	0.51384 (11)	0.84356 (15)	0.0364 (4)
H7	0.0713	0.4678	0.8108	0.044*
C8	0.24959 (19)	0.48391 (11)	0.94849 (16)	0.0351 (4)
C9	0.29187 (19)	0.52757 (11)	1.05297 (16)	0.0370 (4)
C10	0.09369 (19)	0.61784 (12)	0.98350 (15)	0.0369 (4)
C11	0.0227 (2)	0.68872 (12)	1.02260 (17)	0.0437 (5)
H11A	0.0955	0.7254	1.0686	0.052*
H11B	−0.0348	0.6692	1.0721	0.052*
C12	−0.0740 (2)	0.73612 (12)	0.91906 (17)	0.0420 (5)
C13	−0.1698 (2)	0.67469 (13)	0.83584 (18)	0.0454 (5)
H13A	−0.2407	0.6538	0.8723	0.054*
H13B	−0.2212	0.7035	0.7654	0.054*
C14	−0.0921 (2)	0.60304 (12)	0.80176 (17)	0.0408 (5)
C15	0.04735 (19)	0.57886 (11)	0.88193 (15)	0.0349 (4)
C16	0.4646 (3)	0.7040 (2)	0.5103 (3)	0.0911 (10)
H16A	0.4193	0.7489	0.5382	0.137*
H16B	0.4845	0.7193	0.4386	0.137*
H16C	0.5529	0.6903	0.5675	0.137*
C17	0.4303 (3)	0.55740 (15)	1.25477 (19)	0.0601 (6)
H17A	0.4608	0.6116	1.2410	0.090*
H17B	0.5060	0.5305	1.3124	0.090*
H17C	0.3463	0.5610	1.2824	0.090*
C18	−0.1656 (3)	0.79636 (15)	0.9648 (2)	0.0601 (6)
H18A	−0.2291	0.8249	0.9004	0.090*
H18B	−0.1043	0.8352	1.0158	0.090*
H18C	−0.2211	0.7670	1.0071	0.090*
C19	0.0178 (2)	0.78296 (13)	0.85468 (19)	0.0513 (5)
H19A	−0.0437	0.8135	0.7914	0.077*
H19B	0.0739	0.7448	0.8244	0.077*
H19C	0.0807	0.8199	0.9078	0.077*
N1	0.39661 (17)	0.51069 (10)	1.14645 (13)	0.0440 (4)
H1	0.4495	0.4688	1.1436	0.053*
N2	0.32201 (17)	0.41331 (10)	0.93523 (14)	0.0408 (4)
O1	0.21955 (14)	0.59653 (8)	1.06663 (11)	0.0443 (4)
O2	0.28171 (16)	0.37471 (9)	0.84138 (13)	0.0546 (4)
O3	0.42684 (15)	0.38750 (9)	1.01655 (13)	0.0517 (4)
O4	−0.14344 (16)	0.56445 (10)	0.71241 (13)	0.0605 (4)
O5	0.37227 (17)	0.63553 (10)	0.49054 (13)	0.0606 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0398 (10)	0.0504 (12)	0.0366 (11)	0.0007 (9)	0.0128 (8)	0.0035 (9)
C2	0.0412 (11)	0.0462 (12)	0.0436 (12)	−0.0084 (9)	0.0110 (9)	−0.0018 (9)
C3	0.0432 (11)	0.0445 (11)	0.0322 (10)	−0.0045 (9)	0.0081 (8)	−0.0080 (8)
C4	0.0346 (9)	0.0337 (10)	0.0323 (10)	0.0019 (7)	0.0078 (7)	−0.0001 (8)
C5	0.0441 (11)	0.0368 (10)	0.0365 (11)	−0.0061 (8)	0.0084 (8)	−0.0053 (8)
C6	0.0526 (12)	0.0500 (12)	0.0319 (11)	−0.0018 (10)	0.0107 (9)	−0.0061 (9)
C7	0.0386 (10)	0.0352 (10)	0.0342 (10)	−0.0030 (8)	0.0082 (8)	−0.0022 (8)
C8	0.0391 (10)	0.0317 (10)	0.0351 (10)	0.0025 (8)	0.0112 (8)	0.0024 (8)
C9	0.0372 (10)	0.0366 (10)	0.0375 (11)	0.0015 (8)	0.0111 (8)	0.0043 (8)
C10	0.0376 (10)	0.0406 (11)	0.0317 (10)	0.0042 (8)	0.0085 (8)	0.0035 (8)
C11	0.0490 (11)	0.0441 (11)	0.0385 (11)	0.0079 (9)	0.0132 (9)	−0.0005 (9)
C12	0.0412 (10)	0.0443 (11)	0.0417 (11)	0.0070 (9)	0.0134 (9)	0.0036 (9)
C13	0.0341 (10)	0.0528 (12)	0.0486 (12)	0.0027 (9)	0.0103 (9)	0.0055 (10)
C14	0.0364 (10)	0.0482 (11)	0.0375 (11)	−0.0051 (9)	0.0097 (8)	0.0009 (9)
C15	0.0351 (9)	0.0360 (10)	0.0336 (10)	−0.0014 (8)	0.0094 (8)	0.0016 (8)
C16	0.091 (2)	0.115 (3)	0.0780 (19)	−0.0483 (19)	0.0415 (16)	0.0042 (18)
C17	0.0600 (14)	0.0704 (16)	0.0411 (12)	0.0102 (12)	−0.0009 (10)	−0.0052 (11)
C18	0.0615 (14)	0.0553 (14)	0.0684 (15)	0.0178 (11)	0.0262 (12)	0.0044 (12)
C19	0.0532 (12)	0.0467 (12)	0.0553 (13)	−0.0012 (10)	0.0174 (10)	0.0075 (10)
N1	0.0428 (9)	0.0486 (10)	0.0372 (9)	0.0080 (8)	0.0055 (7)	0.0017 (8)
N2	0.0439 (9)	0.0375 (9)	0.0428 (10)	0.0028 (7)	0.0149 (8)	0.0026 (8)
O1	0.0483 (8)	0.0448 (8)	0.0339 (7)	0.0104 (6)	0.0015 (6)	−0.0029 (6)
O2	0.0650 (10)	0.0459 (8)	0.0510 (9)	0.0057 (7)	0.0132 (7)	−0.0114 (7)
O3	0.0494 (8)	0.0493 (9)	0.0529 (9)	0.0145 (7)	0.0084 (7)	0.0039 (7)
O4	0.0483 (9)	0.0725 (11)	0.0514 (9)	0.0013 (8)	−0.0017 (7)	−0.0156 (8)
O5	0.0664 (10)	0.0765 (11)	0.0458 (9)	−0.0169 (8)	0.0269 (8)	0.0003 (8)

C1—O5	1.367 (2)	C12—C18	1.522 (3)
C1—C2	1.384 (3)	C12—C13	1.529 (3)
C1—C6	1.386 (3)	C12—C19	1.530 (3)
C2—C3	1.389 (3)	C13—C14	1.505 (3)
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.380 (3)	C13—H13B	0.9700
C3—H3	0.9300	C14—O4	1.218 (2)
C4—C5	1.386 (3)	C14—C15	1.474 (3)
C4—C7	1.528 (2)	C16—O5	1.408 (3)
C5—C6	1.378 (3)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—H6	0.9300	C16—H16C	0.9600
C7—C15	1.504 (3)	C17—N1	1.456 (3)
C7—C8	1.505 (3)	C17—H17A	0.9600
C7—H7	0.9800	C17—H17B	0.9600
C8—N2	1.380 (2)	C17—H17C	0.9600
C8—C9	1.394 (3)	C18—H18A	0.9600
C9—N1	1.311 (2)	C18—H18B	0.9600
C9—O1	1.358 (2)	C18—H18C	0.9600
C10—C15	1.330 (3)	C19—H19A	0.9600
C10—O1	1.384 (2)	C19—H19B	0.9600
C10—C11	1.485 (3)	C19—H19C	0.9600
C11—C12	1.534 (3)	N1—H1	0.8600
C11—H11A	0.9700	N2—O2	1.248 (2)
C11—H11B	0.9700	N2—O3	1.265 (2)
O5—C1—C2	124.08 (18)	C14—C13—C12	115.15 (16)
O5—C1—C6	116.05 (17)	C14—C13—H13A	108.5
C2—C1—C6	119.87 (18)	C12—C13—H13A	108.5
C1—C2—C3	118.87 (18)	C14—C13—H13B	108.5
C1—C2—H2	120.6	C12—C13—H13B	108.5
C3—C2—H2	120.6	H13A—C13—H13B	107.5
C4—C3—C2	122.16 (17)	O4—C14—C15	120.41 (19)
C4—C3—H3	118.9	O4—C14—C13	121.60 (18)
C2—C3—H3	118.9	C15—C14—C13	117.96 (17)
C3—C4—C5	117.75 (17)	C10—C15—C14	118.59 (17)
C3—C4—C7	120.57 (16)	C10—C15—C7	122.52 (16)
C5—C4—C7	121.68 (16)	C14—C15—C7	118.83 (16)
C6—C5—C4	121.28 (18)	O5—C16—H16A	109.5
C6—C5—H5	119.4	O5—C16—H16B	109.5
C4—C5—H5	119.4	H16A—C16—H16B	109.5
C5—C6—C1	120.07 (18)	O5—C16—H16C	109.5
C5—C6—H6	120.0	H16A—C16—H16C	109.5
C1—C6—H6	120.0	H16B—C16—H16C	109.5
C15—C7—C8	108.89 (15)	N1—C17—H17A	109.5
C15—C7—C4	110.20 (15)	N1—C17—H17B	109.5
C8—C7—C4	111.93 (15)	H17A—C17—H17B	109.5
C15—C7—H7	108.6	N1—C17—H17C	109.5
C8—C7—H7	108.6	H17A—C17—H17C	109.5
C4—C7—H7	108.6	H17B—C17—H17C	109.5
N2—C8—C9	119.75 (16)	C12—C18—H18A	109.5
N2—C8—C7	117.19 (16)	C12—C18—H18B	109.5
C9—C8—C7	122.87 (16)	H18A—C18—H18B	109.5
N1—C9—O1	112.01 (16)	C12—C18—H18C	109.5
N1—C9—C8	128.20 (17)	H18A—C18—H18C	109.5
O1—C9—C8	119.79 (16)	H18B—C18—H18C	109.5
C15—C10—O1	122.61 (17)	C12—C19—H19A	109.5
C15—C10—C11	126.11 (17)	C12—C19—H19B	109.5
O1—C10—C11	111.28 (15)	H19A—C19—H19B	109.5
C10—C11—C12	111.81 (16)	C12—C19—H19C	109.5
C10—C11—H11A	109.3	H19A—C19—H19C	109.5
C12—C11—H11A	109.3	H19B—C19—H19C	109.5
C10—C11—H11B	109.3	C9—N1—C17	125.02 (17)
C12—C11—H11B	109.3	C9—N1—H1	117.5
H11A—C11—H11B	107.9	C17—N1—H1	117.5
C18—C12—C13	110.27 (17)	O2—N2—O3	120.24 (16)
C18—C12—C19	109.56 (18)	O2—N2—C8	118.77 (16)
C13—C12—C19	109.51 (16)	O3—N2—C8	120.99 (16)
C18—C12—C11	108.80 (17)	C9—O1—C10	120.16 (14)
C13—C12—C11	108.45 (16)	C1—O5—C16	118.32 (18)
C19—C12—C11	110.24 (16)
O5—C1—C2—C3	179.89 (18)	C19—C12—C13—C14	69.9 (2)
C6—C1—C2—C3	0.1 (3)	C11—C12—C13—C14	−50.4 (2)
C1—C2—C3—C4	0.3 (3)	C12—C13—C14—O4	−157.06 (19)
C2—C3—C4—C5	−1.1 (3)	C12—C13—C14—C15	24.8 (3)
C2—C3—C4—C7	179.10 (17)	O1—C10—C15—C14	176.63 (16)
C3—C4—C5—C6	1.4 (3)	C11—C10—C15—C14	−4.4 (3)
C7—C4—C5—C6	−178.82 (17)	O1—C10—C15—C7	−6.2 (3)
C4—C5—C6—C1	−0.9 (3)	C11—C10—C15—C7	172.76 (18)
O5—C1—C6—C5	−179.63 (18)	O4—C14—C15—C10	−174.04 (19)
C2—C1—C6—C5	0.1 (3)	C13—C14—C15—C10	4.1 (3)
C3—C4—C7—C15	60.8 (2)	O4—C14—C15—C7	8.7 (3)
C5—C4—C7—C15	−119.02 (18)	C13—C14—C15—C7	−173.13 (16)
C3—C4—C7—C8	−60.5 (2)	C8—C7—C15—C10	17.8 (2)
C5—C4—C7—C8	119.66 (19)	C4—C7—C15—C10	−105.4 (2)
C15—C7—C8—N2	167.42 (15)	C8—C7—C15—C14	−165.09 (16)
C4—C7—C8—N2	−70.5 (2)	C4—C7—C15—C14	71.8 (2)
C15—C7—C8—C9	−17.7 (2)	O1—C9—N1—C17	2.2 (3)
C4—C7—C8—C9	104.4 (2)	C8—C9—N1—C17	−177.0 (2)
N2—C8—C9—N1	0.0 (3)	C9—C8—N2—O2	179.39 (17)
C7—C8—C9—N1	−174.71 (18)	C7—C8—N2—O2	−5.6 (2)
N2—C8—C9—O1	−179.21 (16)	C9—C8—N2—O3	−0.2 (3)
C7—C8—C9—O1	6.1 (3)	C7—C8—N2—O3	174.84 (16)
C15—C10—C11—C12	−23.7 (3)	N1—C9—O1—C10	−171.21 (16)
O1—C10—C11—C12	155.32 (16)	C8—C9—O1—C10	8.1 (3)
C10—C11—C12—C18	168.69 (17)	C15—C10—O1—C9	−8.3 (3)
C10—C11—C12—C13	48.7 (2)	C11—C10—O1—C9	172.65 (16)
C10—C11—C12—C19	−71.2 (2)	C2—C1—O5—C16	−1.8 (3)
C18—C12—C13—C14	−169.46 (17)	C6—C1—O5—C16	178.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···Cg2i	0.96	2.78	3.652	142
N1—H1···O3	0.86	1.98	2.602 (2)	128

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17B⋯Cg2i	0.96	2.78	3.652	142
N1—H1⋯O3	0.86	1.98	2.602 (2)	128

Symmetry code: (i) .