6-Ethyl-N-methyl-3-nitro-4-nitro-methyl-4H-chromen-2-amine.

In the title compound, C(13)H(15)N(3)O(5), the O and N atoms of the nitro-methyl group and the methyl C atom of the ethyl group are disordered over two sets of sites with refined occupancies of 0.629 (7):0.371 (7) and 0.533 (8):0.467 (8), respectively. The dihydro-pyran ring has an extremely flattened conformation. An intra-molecular N-H⋯O hydrogen bond occurs. In the crystal, pairs of N-H⋯O hydrogen bonds link mol-ecules, forming inversion dimers. In addition, weak inter-molecular C-H⋯O hydrogen bonds are also present.

Related literature

For the biological and pharmacological importance of 4H-chromene derivatives, see: Cai (2007 ▶, 2008 ▶); Cai et al. (2006 ▶); Gabor (1988 ▶); Brooks (1998 ▶); Hyana & Saimoto (1987 ▶); Tang et al. (2007 ▶). For related structures, see: Muthukumaran et al. (2011a ▶,b ▶,c ▶); Gayathri et al. (2006 ▶); Bhaskaran et al. (2006 ▶).

Experimental

Crystal data

C13H15N3O5

M = 293.28

Triclinic,

a = 8.2538 (10) Å

b = 9.0431 (9) Å

c = 10.3323 (12) Å

α = 73.484 (9)°

β = 71.728 (11)°

γ = 83.234 (9)°

V = 701.75 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.4 × 0.35 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.958, T max = 0.979

4281 measured reflections

2463 independent reflections

1520 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.232

S = 1.06

2463 reflections

205 parameters

122 restraints

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.34 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053554/lh5388sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053554/lh5388Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053554/lh5388Isup3.cml

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

C13H15N3O5	Z = 2
Mr = 293.28	F(000) = 308
Triclinic, P1	Dx = 1.388 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2538 (10) Å	Cell parameters from 1935 reflections
b = 9.0431 (9) Å	θ = 2.7–29.1°
c = 10.3323 (12) Å	µ = 0.11 mm−1
α = 73.484 (9)°	T = 293 K
β = 71.728 (11)°	Block, colorless
γ = 83.234 (9)°	0.4 × 0.35 × 0.2 mm
V = 701.75 (14) Å3

Oxford Diffraction Xcalibur Eos diffractometer	2463 independent reflections
Radiation source: fine-focus sealed tube	1520 reflections with I > 2σ(I)
graphite	Rint = 0.031
Detector resolution: 15.9821 pixels mm-1	θmax = 25.0°, θmin = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→10
Tmin = 0.958, Tmax = 0.979	l = −11→12
4281 measured reflections

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.232	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1377P)2 + 0.1022P] where P = (Fo2 + 2Fc2)/3
2463 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.40 e Å−3
122 restraints	Δρmin = −0.34 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)
O1	0.4139 (2)	0.2857 (3)	1.1942 (2)	0.0468 (6)
C1	0.5007 (4)	0.2700 (4)	1.0581 (3)	0.0401 (8)
C8	0.6569 (4)	0.4021 (4)	1.1982 (3)	0.0383 (8)
O2	0.6415 (3)	0.5176 (3)	1.3724 (2)	0.0569 (7)
O3	0.8792 (3)	0.5209 (3)	1.2039 (2)	0.0636 (8)
N2	0.7266 (3)	0.4819 (3)	1.2608 (3)	0.0435 (7)
C9	0.4856 (4)	0.3561 (4)	1.2598 (3)	0.0394 (8)
N1	0.3831 (3)	0.3738 (3)	1.3790 (3)	0.0490 (8)
H1	0.4224	0.4167	1.4267	0.059*
C6	0.6684 (4)	0.3088 (4)	0.9922 (3)	0.0380 (8)
C2	0.4066 (4)	0.2138 (4)	0.9941 (4)	0.0490 (9)
H2	0.2935	0.1877	1.0408	0.059*
C5	0.7416 (4)	0.2899 (4)	0.8563 (3)	0.0489 (9)
H5	0.8551	0.3151	0.8099	0.059*
C7	0.7700 (4)	0.3607 (4)	1.0681 (3)	0.0413 (8)
H7	0.8238	0.4563	1.0044	0.050*
C4	0.6519 (5)	0.2354 (4)	0.7888 (4)	0.0528 (9)
C3	0.4833 (5)	0.1970 (4)	0.8600 (4)	0.0548 (10)
H3	0.4209	0.1592	0.8160	0.066*
C11	0.9145 (4)	0.2466 (4)	1.0924 (4)	0.0588 (10)
H11A	0.9964	0.2440	1.0021	0.071*
H11B	0.9726	0.2804	1.1468	0.071*
N3A	0.8506 (10)	0.0891 (5)	1.1687 (9)	0.085 (2)	0.629 (7)
O4A	0.7196 (14)	0.0755 (17)	1.2654 (17)	0.113 (3)	0.629 (7)
O5A	0.9064 (12)	−0.0297 (9)	1.1366 (11)	0.169 (3)	0.629 (7)
N3B	0.8580 (16)	0.0962 (10)	1.1944 (16)	0.085 (2)	0.371 (7)
O4B	0.717 (2)	0.043 (3)	1.240 (3)	0.113 (3)	0.371 (7)
O5B	0.9759 (19)	0.0179 (16)	1.2268 (18)	0.169 (3)	0.371 (7)
C12	0.7376 (6)	0.2240 (6)	0.6386 (4)	0.0778 (13)
H12A	0.7279	0.3246	0.5751	0.093*	0.533 (8)
H12B	0.8581	0.2008	0.6277	0.093*	0.533 (8)
H12C	0.6550	0.2506	0.5857	0.093*	0.467 (8)
H12D	0.8286	0.2970	0.5932	0.093*	0.467 (8)
C13A	0.6702 (15)	0.1062 (12)	0.5913 (10)	0.114 (3)	0.533 (8)
H13A	0.7334	0.1097	0.4951	0.171*	0.533 (8)
H13B	0.5517	0.1291	0.5983	0.171*	0.533 (8)
H13C	0.6828	0.0050	0.6506	0.171*	0.533 (8)
C13B	0.8100 (18)	0.0627 (8)	0.6369 (12)	0.114 (3)	0.467 (8)
H13D	0.8636	0.0583	0.5411	0.171*	0.467 (8)
H13E	0.7197	−0.0094	0.6804	0.171*	0.467 (8)
H13F	0.8929	0.0369	0.6881	0.171*	0.467 (8)
C10	0.2057 (4)	0.3261 (6)	1.4383 (4)	0.0722 (13)
H10A	0.1380	0.3912	1.3825	0.108*
H10B	0.1624	0.3350	1.5336	0.108*
H10C	0.2001	0.2209	1.4376	0.108*

	U11	U22	U33	U12	U13	U23
O1	0.0348 (11)	0.0592 (17)	0.0485 (13)	−0.0089 (10)	−0.0032 (9)	−0.0247 (11)
C1	0.0371 (16)	0.041 (2)	0.0445 (17)	0.0043 (14)	−0.0130 (14)	−0.0158 (14)
C8	0.0367 (16)	0.039 (2)	0.0394 (16)	−0.0034 (13)	−0.0094 (13)	−0.0109 (14)
O2	0.0646 (15)	0.0694 (19)	0.0409 (12)	−0.0110 (13)	−0.0074 (11)	−0.0262 (12)
O3	0.0457 (14)	0.085 (2)	0.0667 (16)	−0.0271 (13)	−0.0008 (12)	−0.0383 (15)
N2	0.0472 (16)	0.0450 (18)	0.0393 (14)	−0.0071 (12)	−0.0081 (12)	−0.0155 (13)
C9	0.0362 (16)	0.0365 (19)	0.0431 (17)	0.0004 (13)	−0.0080 (14)	−0.0114 (14)
N1	0.0431 (15)	0.058 (2)	0.0448 (15)	−0.0076 (13)	0.0022 (12)	−0.0255 (14)
C6	0.0404 (17)	0.0360 (19)	0.0386 (16)	0.0007 (13)	−0.0114 (13)	−0.0126 (14)
C2	0.0420 (18)	0.050 (2)	0.063 (2)	0.0021 (15)	−0.0210 (16)	−0.0223 (18)
C5	0.0472 (18)	0.051 (2)	0.0468 (19)	−0.0022 (16)	−0.0073 (15)	−0.0175 (16)
C7	0.0361 (16)	0.047 (2)	0.0416 (17)	−0.0084 (14)	−0.0050 (13)	−0.0173 (15)
C4	0.064 (2)	0.052 (2)	0.0476 (19)	0.0046 (17)	−0.0212 (17)	−0.0185 (17)
C3	0.066 (2)	0.050 (2)	0.063 (2)	0.0010 (18)	−0.0350 (19)	−0.0208 (18)
C11	0.0356 (17)	0.080 (3)	0.074 (2)	0.0052 (17)	−0.0169 (16)	−0.042 (2)
N3A	0.075 (3)	0.079 (3)	0.095 (4)	0.044 (2)	−0.033 (2)	−0.023 (2)
O4A	0.131 (3)	0.045 (7)	0.154 (7)	−0.008 (3)	−0.030 (3)	−0.021 (4)
O5A	0.189 (6)	0.098 (5)	0.222 (9)	0.055 (5)	−0.065 (5)	−0.065 (5)
N3B	0.075 (3)	0.079 (3)	0.095 (4)	0.044 (2)	−0.033 (2)	−0.023 (2)
O4B	0.131 (3)	0.045 (7)	0.154 (7)	−0.008 (3)	−0.030 (3)	−0.021 (4)
O5B	0.189 (6)	0.098 (5)	0.222 (9)	0.055 (5)	−0.065 (5)	−0.065 (5)
C12	0.100 (3)	0.084 (3)	0.056 (2)	−0.003 (3)	−0.022 (2)	−0.031 (2)
C13A	0.168 (10)	0.096 (6)	0.073 (5)	−0.015 (6)	0.000 (5)	−0.049 (4)
C13B	0.168 (10)	0.096 (6)	0.073 (5)	−0.015 (6)	0.000 (5)	−0.049 (4)
C10	0.046 (2)	0.092 (4)	0.073 (3)	−0.015 (2)	0.0122 (19)	−0.041 (2)

O1—C9	1.342 (4)	C11—N3B	1.4847 (11)
O1—C1	1.403 (3)	C11—N3A	1.4847 (11)
C1—C6	1.375 (4)	C11—H11A	0.9700
C1—C2	1.380 (4)	C11—H11B	0.9700
C8—N2	1.366 (4)	N3A—O4A	1.2113 (11)
C8—C9	1.414 (4)	N3A—O5A	1.2115 (11)
C8—C7	1.496 (4)	N3B—O4B	1.2114 (11)
O2—N2	1.256 (3)	N3B—O5B	1.2117 (11)
O3—N2	1.256 (3)	C12—C13B	1.5122 (11)
C9—N1	1.298 (4)	C12—C13A	1.5125 (11)
N1—C10	1.463 (4)	C12—H12A	0.9700
N1—H1	0.8600	C12—H12B	0.9700
C6—C5	1.395 (4)	C12—H12C	0.9700
C6—C7	1.501 (4)	C12—H12D	0.9700
C2—C3	1.376 (5)	C13A—H13A	0.9600
C2—H2	0.9300	C13A—H13B	0.9600
C5—C4	1.372 (5)	C13A—H13C	0.9600
C5—H5	0.9300	C13B—H13D	0.9600
C7—C11	1.517 (5)	C13B—H13E	0.9600
C7—H7	0.9800	C13B—H13F	0.9600
C4—C3	1.387 (5)	C10—H10A	0.9600
C4—C12	1.518 (5)	C10—H10B	0.9600
C3—H3	0.9300	C10—H10C	0.9600
C9—O1—C1	120.9 (2)	O4A—N3A—O5A	114.3 (8)
C6—C1—C2	122.1 (3)	O4A—N3A—C11	118.5 (9)
C6—C1—O1	122.2 (3)	O5A—N3A—C11	126.8 (8)
C2—C1—O1	115.7 (3)	O4B—N3B—O5B	118.9 (19)
N2—C8—C9	120.1 (3)	O4B—N3B—C11	128.9 (19)
N2—C8—C7	117.6 (2)	O5B—N3B—C11	112.1 (11)
C9—C8—C7	122.2 (3)	C13B—C12—C13A	53.2 (7)
O3—N2—O2	119.8 (3)	C13B—C12—C4	110.9 (5)
O3—N2—C8	118.7 (2)	C13A—C12—C4	116.9 (5)
O2—N2—C8	121.5 (3)	C13B—C12—H12A	141.0
N1—C9—O1	113.2 (3)	C13A—C12—H12A	108.1
N1—C9—C8	126.7 (3)	C4—C12—H12A	108.1
O1—C9—C8	120.1 (3)	C13B—C12—H12B	59.8
C9—N1—C10	125.0 (3)	C13A—C12—H12B	108.1
C9—N1—H1	117.5	C4—C12—H12B	108.1
C10—N1—H1	117.5	H12A—C12—H12B	107.3
C1—C6—C5	117.5 (3)	C13B—C12—H12C	109.5
C1—C6—C7	120.6 (3)	C13A—C12—H12C	57.4
C5—C6—C7	121.8 (3)	C4—C12—H12C	109.5
C3—C2—C1	118.7 (3)	H12A—C12—H12C	56.1
C3—C2—H2	120.6	H12B—C12—H12C	142.2
C1—C2—H2	120.6	C13B—C12—H12D	109.5
C4—C5—C6	122.2 (3)	C13A—C12—H12D	133.6
C4—C5—H5	118.9	C4—C12—H12D	109.5
C6—C5—H5	118.9	H12A—C12—H12D	55.3
C8—C7—C6	111.4 (2)	H12B—C12—H12D	53.9
C8—C7—C11	114.3 (3)	H12C—C12—H12D	108.0
C6—C7—C11	111.6 (3)	C12—C13A—H13A	109.5
C8—C7—H7	106.3	C12—C13A—H13B	109.5
C6—C7—H7	106.3	H13A—C13A—H13B	109.5
C11—C7—H7	106.3	C12—C13A—H13C	109.5
C5—C4—C3	118.2 (3)	H13A—C13A—H13C	109.5
C5—C4—C12	119.3 (3)	H13B—C13A—H13C	109.5
C3—C4—C12	122.5 (3)	C12—C13B—H13D	109.5
C2—C3—C4	121.4 (3)	C12—C13B—H13E	109.5
C2—C3—H3	119.3	H13D—C13B—H13E	109.5
C4—C3—H3	119.3	C12—C13B—H13F	109.5
N3B—C11—C7	114.4 (6)	H13D—C13B—H13F	109.5
N3A—C11—C7	111.4 (4)	H13E—C13B—H13F	109.5
N3B—C11—H11A	117.3	N1—C10—H10A	109.5
N3A—C11—H11A	109.3	N1—C10—H10B	109.5
C7—C11—H11A	109.3	H10A—C10—H10B	109.5
N3B—C11—H11B	97.5	N1—C10—H10C	109.5
N3A—C11—H11B	109.3	H10A—C10—H10C	109.5
C7—C11—H11B	109.3	H10B—C10—H10C	109.5
H11A—C11—H11B	108.0
C9—O1—C1—C6	7.7 (5)	C1—C6—C7—C8	−14.8 (4)
C9—O1—C1—C2	−172.0 (3)	C5—C6—C7—C8	168.7 (3)
C9—C8—N2—O3	179.8 (3)	C1—C6—C7—C11	114.3 (3)
C7—C8—N2—O3	2.4 (4)	C5—C6—C7—C11	−62.2 (4)
C9—C8—N2—O2	−0.7 (5)	C6—C5—C4—C3	−0.6 (5)
C7—C8—N2—O2	−178.2 (3)	C6—C5—C4—C12	177.5 (3)
C1—O1—C9—N1	174.0 (3)	C1—C2—C3—C4	0.0 (5)
C1—O1—C9—C8	−6.3 (4)	C5—C4—C3—C2	0.4 (6)
N2—C8—C9—N1	−4.2 (5)	C12—C4—C3—C2	−177.5 (4)
C7—C8—C9—N1	173.1 (3)	C8—C7—C11—N3B	59.4 (9)
N2—C8—C9—O1	176.1 (3)	C6—C7—C11—N3B	−68.2 (9)
C7—C8—C9—O1	−6.6 (5)	C8—C7—C11—N3A	72.3 (5)
O1—C9—N1—C10	−1.1 (5)	C6—C7—C11—N3A	−55.3 (5)
C8—C9—N1—C10	179.2 (4)	N3B—C11—N3A—O4A	65 (4)
C2—C1—C6—C5	0.3 (5)	C7—C11—N3A—O4A	−41.2 (12)
O1—C1—C6—C5	−179.4 (3)	N3B—C11—N3A—O5A	−123 (4)
C2—C1—C6—C7	−176.3 (3)	C7—C11—N3A—O5A	131.0 (10)
O1—C1—C6—C7	4.0 (5)	N3A—C11—N3B—O4B	−64 (4)
C6—C1—C2—C3	−0.4 (5)	C7—C11—N3B—O4B	15 (2)
O1—C1—C2—C3	179.3 (3)	N3A—C11—N3B—O5B	112 (4)
C1—C6—C5—C4	0.2 (5)	C7—C11—N3B—O5B	−169.6 (13)
C7—C6—C5—C4	176.8 (3)	C5—C4—C12—C13B	96.2 (7)
N2—C8—C7—C6	−166.3 (3)	C3—C4—C12—C13B	−85.9 (8)
C9—C8—C7—C6	16.4 (4)	C5—C4—C12—C13A	154.5 (7)
N2—C8—C7—C11	66.0 (4)	C3—C4—C12—C13A	−27.5 (8)
C9—C8—C7—C11	−111.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.97	2.600 (3)	129
N1—H1···O2i	0.86	2.21	2.943 (4)	143
C11—H11A···O3ii	0.97	2.58	3.258 (4)	128
C12—H12A···O2iii	0.97	2.55	3.457 (5)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.97	2.600 (3)	129
N1—H1⋯O2i	0.86	2.21	2.943 (4)	143
C11—H11A⋯O3ii	0.97	2.58	3.258 (4)	128
C12—H12A⋯O2iii	0.97	2.55	3.457 (5)	156

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