Crystal structure of 2-methyl-amino-3-nitro-4-p-tolyl-pyrano[3,2-c]chromen-5(4H)-one.

In the racemic title compound, C20H16N2O5, the pyran ring adopts a shallow envelope conformation, with the stereogenic C atom displaced from the other atoms by 0.273 (2) Å. The dihedral angle between the fused-ring system and the pendant p-tolyl group is 87.62 (7)°. The mol-ecular conformation is consolidated by an intra-molecular N-H⋯O hydrogen bond, which generates an S(6) ring. In the crystal, mol-ecules are linked by C-H⋯O inter-actions, resulting in [010] chains.

Related literature

For background to the biological activity of chromene derivatives, see: Borges et al. (2005 ▸, 2009 ▸); Gibbs (2000 ▸); Varmus (2006 ▸). For a related structure, see: Narayanan et al. (2013 ▸).

Experimental

Crystal data

C20H16N2O5

M = 364.35

Monoclinic,

a = 10.8336 (11) Å

b = 11.7927 (11) Å

c = 13.7275 (14) Å

β = 108.357 (2)°

V = 1664.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.21 × 0.19 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.978, T max = 0.981

28712 measured reflections

4571 independent reflections

2862 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.151

S = 1.03

4571 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.36 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/S205698901500225X/hb7345sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500225X/hb7345Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500225X/hb7345Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500225X/hb7345fig1.tif

The mol­ecular structure of the title mol­ecule, with atom displacement ellipsoids drawn at the 30% probability level. The intra­molecular N—H⋯O hydrogen bond, which generates an S(6) ring motif, is shown as a dashed line.

Click here for additional data file.

b C . DOI: 10.1107/S205698901500225X/hb7345fig2.tif

The crystal packing of the title compound, viewed along the b axis, showing C9—H9C⋯O4 hydrogen bonds producing chains parallel to the 101 planes.

CCDC reference: 1046918

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

C20H16N2O5	F(000) = 760
Mr = 364.35	Dx = 1.454 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2862 reflections
a = 10.8336 (11) Å	θ = 2.1–30.3°
b = 11.7927 (11) Å	µ = 0.11 mm−1
c = 13.7275 (14) Å	T = 293 K
β = 108.357 (2)°	Block, colourless
V = 1664.5 (3) Å3	0.21 × 0.19 × 0.18 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	4571 independent reflections
Radiation source: fine-focus sealed tube	2862 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω and φ scans	θmax = 30.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.978, Tmax = 0.981	k = −15→16
28712 measured reflections	l = −19→19

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0607P)2 + 0.7266P] where P = (Fo2 + 2Fc2)/3
4571 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.36 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	0.39731 (17)	0.29273 (15)	0.11931 (14)	0.0394 (4)
C2	0.3614 (2)	0.18037 (17)	0.11445 (17)	0.0525 (5)
H2	0.2802	0.1594	0.1181	0.063*
C3	0.4481 (2)	0.09986 (18)	0.10411 (18)	0.0569 (6)
H3	0.4256	0.0235	0.1014	0.068*
C4	0.5677 (2)	0.13063 (17)	0.09769 (17)	0.0538 (5)
H4	0.6246	0.0751	0.0895	0.065*
C5	0.60377 (19)	0.24263 (17)	0.10328 (15)	0.0455 (4)
H5	0.6849	0.2629	0.0990	0.055*
C6	0.51827 (16)	0.32599 (14)	0.11533 (13)	0.0358 (4)
C7	0.54773 (16)	0.44453 (14)	0.13040 (13)	0.0342 (4)
C8	0.70721 (17)	0.58447 (15)	0.13873 (13)	0.0375 (4)
C9	0.9063 (2)	0.5072 (2)	0.11560 (18)	0.0560 (5)
H9A	0.9850	0.5386	0.1089	0.084*
H9B	0.8626	0.4640	0.0553	0.084*
H9C	0.9270	0.4587	0.1747	0.084*
C10	0.62572 (17)	0.66705 (14)	0.15559 (13)	0.0365 (4)
C11	0.50320 (16)	0.64000 (14)	0.18012 (13)	0.0359 (4)
H11	0.4340	0.6918	0.1422	0.043*
C12	0.46442 (16)	0.52058 (15)	0.14680 (13)	0.0350 (4)
C13	0.33590 (17)	0.48409 (16)	0.14373 (14)	0.0422 (4)
C14	0.52303 (15)	0.65125 (14)	0.29503 (13)	0.0331 (4)
C15	0.60210 (17)	0.57475 (15)	0.36318 (14)	0.0400 (4)
H15	0.6410	0.5159	0.3384	0.048*
C16	0.62389 (18)	0.58497 (16)	0.46753 (15)	0.0445 (4)
H16	0.6773	0.5328	0.5120	0.053*
C17	0.56764 (17)	0.67147 (16)	0.50698 (14)	0.0414 (4)
C18	0.5931 (2)	0.6825 (2)	0.62041 (16)	0.0597 (6)
H18A	0.6515	0.6236	0.6554	0.090*
H18B	0.5127	0.6760	0.6354	0.090*
H18C	0.6316	0.7552	0.6431	0.090*
C19	0.48681 (18)	0.74572 (16)	0.43833 (15)	0.0449 (4)
H19	0.4466	0.8037	0.4630	0.054*
C20	0.46409 (17)	0.73612 (15)	0.33388 (14)	0.0405 (4)
H20	0.4087	0.7872	0.2894	0.049*
N1	0.82208 (16)	0.59828 (15)	0.12756 (13)	0.0480 (4)
H1	0.8497	0.6666	0.1273	0.058*
N2	0.66129 (17)	0.78014 (13)	0.15862 (12)	0.0455 (4)
O1	0.67089 (11)	0.47326 (10)	0.13148 (10)	0.0405 (3)
O2	0.30759 (12)	0.37082 (11)	0.12920 (11)	0.0469 (3)
O3	0.25155 (13)	0.54490 (13)	0.15308 (14)	0.0624 (4)
O4	0.58643 (16)	0.85218 (12)	0.17480 (12)	0.0591 (4)
O5	0.76697 (15)	0.80934 (12)	0.14575 (12)	0.0598 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0360 (9)	0.0392 (9)	0.0391 (9)	0.0006 (7)	0.0063 (7)	−0.0084 (7)
C2	0.0418 (10)	0.0437 (11)	0.0668 (14)	−0.0075 (8)	0.0098 (9)	−0.0126 (10)
C3	0.0534 (12)	0.0367 (10)	0.0722 (15)	−0.0048 (9)	0.0077 (10)	−0.0144 (10)
C4	0.0517 (12)	0.0410 (11)	0.0642 (13)	0.0066 (9)	0.0117 (10)	−0.0147 (9)
C5	0.0421 (10)	0.0443 (11)	0.0492 (11)	0.0049 (8)	0.0129 (8)	−0.0096 (8)
C6	0.0367 (9)	0.0356 (9)	0.0325 (9)	0.0017 (7)	0.0073 (7)	−0.0051 (7)
C7	0.0324 (8)	0.0367 (9)	0.0324 (8)	0.0011 (7)	0.0089 (7)	−0.0012 (7)
C8	0.0418 (9)	0.0384 (9)	0.0338 (9)	0.0000 (7)	0.0140 (7)	0.0048 (7)
C9	0.0470 (11)	0.0626 (13)	0.0669 (14)	0.0091 (10)	0.0301 (10)	0.0089 (11)
C10	0.0412 (9)	0.0320 (8)	0.0374 (9)	0.0011 (7)	0.0139 (7)	0.0033 (7)
C11	0.0342 (8)	0.0303 (8)	0.0417 (9)	0.0059 (7)	0.0097 (7)	0.0013 (7)
C12	0.0332 (8)	0.0357 (9)	0.0342 (9)	0.0034 (7)	0.0079 (7)	−0.0016 (7)
C13	0.0346 (9)	0.0415 (10)	0.0470 (10)	0.0018 (7)	0.0081 (8)	−0.0061 (8)
C14	0.0298 (8)	0.0308 (8)	0.0402 (9)	−0.0002 (6)	0.0131 (7)	−0.0001 (7)
C15	0.0393 (9)	0.0360 (9)	0.0457 (10)	0.0082 (7)	0.0149 (8)	−0.0012 (7)
C16	0.0436 (10)	0.0439 (10)	0.0438 (10)	0.0067 (8)	0.0107 (8)	0.0084 (8)
C17	0.0385 (9)	0.0442 (10)	0.0441 (10)	−0.0077 (8)	0.0165 (8)	−0.0041 (8)
C18	0.0679 (14)	0.0687 (15)	0.0450 (12)	−0.0062 (11)	0.0212 (10)	−0.0041 (10)
C19	0.0460 (10)	0.0415 (10)	0.0517 (11)	0.0046 (8)	0.0220 (9)	−0.0075 (8)
C20	0.0385 (9)	0.0366 (9)	0.0466 (10)	0.0071 (7)	0.0138 (8)	−0.0001 (8)
N1	0.0472 (9)	0.0462 (9)	0.0595 (10)	−0.0008 (7)	0.0295 (8)	0.0051 (8)
N2	0.0586 (10)	0.0366 (8)	0.0424 (9)	−0.0015 (7)	0.0176 (8)	0.0045 (7)
O1	0.0364 (6)	0.0360 (7)	0.0525 (8)	0.0021 (5)	0.0189 (6)	−0.0005 (6)
O2	0.0344 (6)	0.0419 (7)	0.0626 (9)	−0.0018 (5)	0.0129 (6)	−0.0120 (6)
O3	0.0376 (7)	0.0541 (9)	0.0952 (12)	0.0077 (6)	0.0204 (8)	−0.0142 (8)
O4	0.0780 (10)	0.0349 (7)	0.0708 (10)	0.0064 (7)	0.0328 (8)	0.0035 (7)
O5	0.0682 (10)	0.0461 (8)	0.0738 (11)	−0.0111 (7)	0.0348 (8)	0.0063 (7)

C1—O2	1.376 (2)	C11—C12	1.499 (2)
C1—C2	1.377 (3)	C11—C14	1.529 (2)
C1—C6	1.385 (2)	C11—H11	0.9800
C2—C3	1.374 (3)	C12—C13	1.445 (2)
C2—H2	0.9300	C13—O3	1.200 (2)
C3—C4	1.374 (3)	C13—O2	1.371 (2)
C3—H3	0.9300	C14—C20	1.381 (2)
C4—C5	1.373 (3)	C14—C15	1.385 (2)
C4—H4	0.9300	C15—C16	1.382 (3)
C5—C6	1.396 (2)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.383 (3)
C6—C7	1.434 (2)	C16—H16	0.9300
C7—C12	1.341 (2)	C17—C19	1.379 (3)
C7—O1	1.372 (2)	C17—C18	1.499 (3)
C8—N1	1.311 (2)	C18—H18A	0.9600
C8—O1	1.364 (2)	C18—H18B	0.9600
C8—C10	1.382 (2)	C18—H18C	0.9600
C9—N1	1.452 (3)	C19—C20	1.381 (3)
C9—H9A	0.9600	C19—H19	0.9300
C9—H9B	0.9600	C20—H20	0.9300
C9—H9C	0.9600	N1—H1	0.8600
C10—N2	1.385 (2)	N2—O4	1.242 (2)
C10—C11	1.503 (2)	N2—O5	1.260 (2)
O2—C1—C2	116.81 (17)	C7—C12—C13	119.29 (16)
O2—C1—C6	121.38 (16)	C7—C12—C11	122.74 (15)
C2—C1—C6	121.81 (17)	C13—C12—C11	117.61 (15)
C3—C2—C1	118.54 (19)	O3—C13—O2	117.06 (17)
C3—C2—H2	120.7	O3—C13—C12	125.32 (18)
C1—C2—H2	120.7	O2—C13—C12	117.62 (15)
C2—C3—C4	120.87 (19)	C20—C14—C15	118.29 (16)
C2—C3—H3	119.6	C20—C14—C11	121.95 (15)
C4—C3—H3	119.6	C15—C14—C11	119.76 (15)
C5—C4—C3	120.53 (19)	C16—C15—C14	120.72 (16)
C5—C4—H4	119.7	C16—C15—H15	119.6
C3—C4—H4	119.7	C14—C15—H15	119.6
C4—C5—C6	119.76 (19)	C15—C16—C17	121.18 (17)
C4—C5—H5	120.1	C15—C16—H16	119.4
C6—C5—H5	120.1	C17—C16—H16	119.4
C1—C6—C5	118.46 (17)	C19—C17—C16	117.64 (17)
C1—C6—C7	116.14 (15)	C19—C17—C18	121.61 (18)
C5—C6—C7	125.29 (17)	C16—C17—C18	120.75 (19)
C12—C7—O1	122.46 (16)	C17—C18—H18A	109.5
C12—C7—C6	123.04 (16)	C17—C18—H18B	109.5
O1—C7—C6	114.43 (14)	H18A—C18—H18B	109.5
N1—C8—O1	111.93 (16)	C17—C18—H18C	109.5
N1—C8—C10	127.74 (17)	H18A—C18—H18C	109.5
O1—C8—C10	120.33 (15)	H18B—C18—H18C	109.5
N1—C9—H9A	109.5	C17—C19—C20	121.64 (17)
N1—C9—H9B	109.5	C17—C19—H19	119.2
H9A—C9—H9B	109.5	C20—C19—H19	119.2
N1—C9—H9C	109.5	C19—C20—C14	120.49 (17)
H9A—C9—H9C	109.5	C19—C20—H20	119.8
H9B—C9—H9C	109.5	C14—C20—H20	119.8
C8—C10—N2	119.80 (16)	C8—N1—C9	125.09 (17)
C8—C10—C11	122.95 (15)	C8—N1—H1	117.5
N2—C10—C11	117.04 (15)	C9—N1—H1	117.5
C12—C11—C10	108.26 (14)	O4—N2—O5	120.76 (16)
C12—C11—C14	109.33 (14)	O4—N2—C10	118.21 (16)
C10—C11—C14	111.45 (14)	O5—N2—C10	121.03 (16)
C12—C11—H11	109.3	C8—O1—C7	119.69 (13)
C10—C11—H11	109.3	C13—O2—C1	122.25 (14)
C14—C11—H11	109.3
O2—C1—C2—C3	179.72 (18)	C11—C12—C13—O3	9.9 (3)
C6—C1—C2—C3	−0.8 (3)	C7—C12—C13—O2	3.3 (3)
C1—C2—C3—C4	−0.6 (3)	C11—C12—C13—O2	−169.93 (15)
C2—C3—C4—C5	1.1 (3)	C12—C11—C14—C20	−129.00 (17)
C3—C4—C5—C6	−0.2 (3)	C10—C11—C14—C20	111.35 (18)
O2—C1—C6—C5	−178.80 (16)	C12—C11—C14—C15	51.0 (2)
C2—C1—C6—C5	1.7 (3)	C10—C11—C14—C15	−68.7 (2)
O2—C1—C6—C7	4.9 (2)	C20—C14—C15—C16	−1.6 (3)
C2—C1—C6—C7	−174.59 (18)	C11—C14—C15—C16	178.42 (16)
C4—C5—C6—C1	−1.2 (3)	C14—C15—C16—C17	0.0 (3)
C4—C5—C6—C7	174.73 (18)	C15—C16—C17—C19	1.4 (3)
C1—C6—C7—C12	−0.5 (3)	C15—C16—C17—C18	−179.30 (18)
C5—C6—C7—C12	−176.51 (18)	C16—C17—C19—C20	−1.2 (3)
C1—C6—C7—O1	176.64 (15)	C18—C17—C19—C20	179.47 (18)
C5—C6—C7—O1	0.6 (3)	C17—C19—C20—C14	−0.4 (3)
N1—C8—C10—N2	2.4 (3)	C15—C14—C20—C19	1.8 (3)
O1—C8—C10—N2	−177.36 (15)	C11—C14—C20—C19	−178.26 (16)
N1—C8—C10—C11	−172.24 (17)	O1—C8—N1—C9	−3.8 (3)
O1—C8—C10—C11	8.0 (3)	C10—C8—N1—C9	176.42 (19)
C8—C10—C11—C12	−19.5 (2)	C8—C10—N2—O4	−179.39 (17)
N2—C10—C11—C12	165.70 (15)	C11—C10—N2—O4	−4.5 (2)
C8—C10—C11—C14	100.73 (19)	C8—C10—N2—O5	0.3 (3)
N2—C10—C11—C14	−74.03 (19)	C11—C10—N2—O5	175.25 (16)
O1—C7—C12—C13	179.56 (15)	N1—C8—O1—C7	−173.09 (15)
C6—C7—C12—C13	−3.6 (3)	C10—C8—O1—C7	6.7 (2)
O1—C7—C12—C11	−7.6 (3)	C12—C7—O1—C8	−7.0 (2)
C6—C7—C12—C11	169.29 (16)	C6—C7—O1—C8	175.86 (15)
C10—C11—C12—C7	19.3 (2)	O3—C13—O2—C1	−178.85 (17)
C14—C11—C12—C7	−102.29 (19)	C12—C13—O2—C1	1.0 (3)
C10—C11—C12—C13	−167.72 (15)	C2—C1—O2—C13	174.23 (17)
C14—C11—C12—C13	70.70 (19)	C6—C1—O2—C13	−5.2 (3)
C7—C12—C13—O3	−176.84 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.86	1.96	2.590 (2)	129
C9—H9C···O4i	0.96	2.46	3.389 (3)	163

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1O5	0.86	1.96	2.590(2)	129
C9H9CO4i	0.96	2.46	3.389(3)	163

Symmetry code: (i) .