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

In the title compound, C(12)H(13)N(3)O(6), the dihydro-pyran ring adopts a near screw-boat conformation. The dihedral angle between the mean planes of the benzene and dihydro-pyran rings is 6.35 (5)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) motif, which stabilizes the mol-ecular conformation. In the crystal, weak inter-molecular C-H⋯O, N-H⋯O and C-H⋯π hydrogen bonds contribute to the stabilization of the packing.

Related literature

For related structures, see: Gayathri et al. (2006 ▶); Bhaskaran et al. (2006 ▶). For the biological importance of 4H-chromene derivatives, see: Cai (2007 ▶, 2008 ▶); Cai et al. (2006 ▶); Gabor et al. (1988 ▶); Brooks (1998 ▶); Valenti et al. (1993 ▶); Hyana & Saimoto (1987 ▶); Tang et al. (2007 ▶); Wang et al. (2000 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For C—H⋯π inter­actions, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C12H13N3O6

M = 295.25

Monoclinic,

a = 6.8354 (2) Å

b = 9.4363 (2) Å

c = 19.9332 (4) Å

β = 90.777 (2)°

V = 1285.59 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.4 × 0.4 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.966, T max = 1.000

13856 measured reflections

2256 independent reflections

1804 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.01

2256 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.36 e Å−3

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015595/hq2002sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015595/hq2002Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015595/hq2002Isup3.cml

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

C12H13N3O6	F(000) = 616
Mr = 295.25	Dx = 1.525 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7594 reflections
a = 6.8354 (2) Å	θ = 3.0–29.3°
b = 9.4363 (2) Å	µ = 0.12 mm−1
c = 19.9332 (4) Å	T = 293 K
β = 90.777 (2)°	Block, colorless
V = 1285.59 (5) Å3	0.4 × 0.4 × 0.2 mm
Z = 4

Oxford Diffraction Xcalibur Eos diffractometer	2256 independent reflections
Radiation source: fine-focus sealed tube	1804 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 15.9821 pixels mm-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→11
Tmin = 0.966, Tmax = 1.000	l = −23→23
13856 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.087P)2] where P = (Fo2 + 2Fc2)/3
2256 reflections	(Δ/σ)max = 0.015
192 parameters	Δρmax = 0.28 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.2620 (2)	0.61723 (15)	−0.00254 (7)	0.0299 (4)
C2	0.2708 (2)	0.58244 (17)	−0.06949 (8)	0.0337 (4)
H2	0.2594	0.4884	−0.0830	0.040*
C3	0.2967 (2)	0.68797 (18)	−0.11657 (8)	0.0356 (4)
H3	0.3019	0.6656	−0.1620	0.043*
C4	0.3149 (2)	0.82767 (17)	−0.09555 (8)	0.0335 (4)
C5	0.3093 (2)	0.85951 (17)	−0.02791 (7)	0.0329 (4)
H5	0.3239	0.9532	−0.0142	0.039*
C6	0.2826 (2)	0.75487 (16)	0.01994 (7)	0.0297 (4)
C7	0.2766 (2)	0.78954 (16)	0.09386 (7)	0.0323 (4)
H7	0.3939	0.8453	0.1045	0.039*
C8	0.2891 (2)	0.65553 (16)	0.13472 (7)	0.0310 (4)
C9	0.2506 (2)	0.52117 (16)	0.10765 (7)	0.0289 (4)
C10	0.2007 (2)	0.26444 (16)	0.10926 (9)	0.0379 (4)
H10A	0.0798	0.2655	0.0842	0.057*
H10B	0.1950	0.1928	0.1434	0.057*
H10C	0.3067	0.2442	0.0796	0.057*
C11	0.0974 (3)	0.88254 (16)	0.11164 (8)	0.0379 (4)
H11A	0.1119	0.9171	0.1573	0.046*
H11B	0.0916	0.9638	0.0819	0.046*
C12	0.3430 (3)	0.9162 (2)	−0.20753 (8)	0.0543 (5)
H12A	0.4498	0.8543	−0.2180	0.081*
H12B	0.3585	1.0045	−0.2308	0.081*
H12C	0.2219	0.8728	−0.2213	0.081*
N1	0.2318 (2)	0.40166 (13)	0.14032 (6)	0.0336 (3)
H1	0.2383	0.4048	0.1834	0.040*
N2	0.3329 (2)	0.67051 (14)	0.20171 (6)	0.0356 (3)
N3	−0.0864 (2)	0.80035 (15)	0.10518 (7)	0.0411 (4)
O1	0.22704 (16)	0.50418 (11)	0.04132 (5)	0.0358 (3)
O2	0.3398 (2)	0.56472 (13)	0.24035 (5)	0.0496 (4)
O3	0.3669 (2)	0.79190 (12)	0.22406 (6)	0.0484 (4)
O4	−0.1438 (2)	0.73633 (16)	0.15375 (8)	0.0703 (5)
O5	−0.1686 (2)	0.79552 (16)	0.05057 (7)	0.0641 (4)
O6	0.34105 (19)	0.94142 (13)	−0.13716 (6)	0.0486 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0314 (8)	0.0310 (8)	0.0272 (8)	−0.0014 (6)	0.0001 (6)	0.0012 (7)
C2	0.0359 (9)	0.0344 (9)	0.0307 (9)	−0.0006 (7)	0.0012 (7)	−0.0079 (7)
C3	0.0352 (9)	0.0487 (10)	0.0230 (8)	−0.0021 (7)	0.0032 (7)	−0.0045 (7)
C4	0.0309 (8)	0.0418 (9)	0.0280 (8)	−0.0032 (7)	0.0031 (6)	0.0049 (7)
C5	0.0366 (9)	0.0321 (8)	0.0299 (8)	−0.0033 (7)	0.0004 (7)	0.0001 (7)
C6	0.0321 (8)	0.0318 (8)	0.0253 (8)	−0.0015 (6)	0.0000 (6)	−0.0011 (6)
C7	0.0439 (9)	0.0280 (8)	0.0250 (8)	−0.0055 (7)	−0.0029 (7)	−0.0021 (6)
C8	0.0381 (9)	0.0309 (8)	0.0238 (8)	−0.0002 (7)	−0.0020 (6)	−0.0013 (6)
C9	0.0297 (8)	0.0318 (8)	0.0253 (8)	0.0030 (6)	−0.0003 (6)	−0.0002 (6)
C10	0.0427 (10)	0.0285 (9)	0.0424 (10)	−0.0002 (7)	−0.0050 (8)	−0.0008 (7)
C11	0.0610 (11)	0.0249 (8)	0.0278 (9)	0.0013 (7)	−0.0020 (7)	−0.0042 (7)
C12	0.0661 (13)	0.0703 (14)	0.0267 (9)	−0.0128 (10)	0.0045 (8)	0.0082 (9)
N1	0.0443 (8)	0.0296 (7)	0.0270 (7)	0.0007 (6)	−0.0005 (6)	−0.0001 (6)
N2	0.0455 (8)	0.0358 (8)	0.0254 (7)	−0.0029 (6)	−0.0042 (6)	−0.0010 (6)
N3	0.0534 (9)	0.0347 (8)	0.0353 (9)	0.0109 (6)	0.0022 (7)	−0.0042 (7)
O1	0.0538 (7)	0.0289 (6)	0.0244 (6)	−0.0057 (5)	−0.0031 (5)	−0.0018 (4)
O2	0.0772 (9)	0.0417 (7)	0.0297 (7)	−0.0045 (6)	−0.0105 (6)	0.0074 (5)
O3	0.0775 (9)	0.0378 (7)	0.0297 (7)	−0.0097 (6)	−0.0054 (6)	−0.0087 (5)
O4	0.0762 (10)	0.0754 (10)	0.0597 (9)	−0.0071 (8)	0.0115 (8)	0.0222 (8)
O5	0.0679 (10)	0.0781 (10)	0.0460 (8)	0.0039 (7)	−0.0138 (7)	−0.0154 (7)
O6	0.0696 (9)	0.0479 (7)	0.0285 (6)	−0.0079 (6)	0.0065 (6)	0.0080 (5)

C1—C2	1.376 (2)	C9—O1	1.3394 (17)
C1—C6	1.381 (2)	C10—N1	1.4496 (19)
C1—O1	1.4019 (17)	C10—H10A	0.9600
C2—C3	1.381 (2)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.388 (2)	C11—N3	1.480 (2)
C3—H3	0.9300	C11—H11A	0.9700
C4—O6	1.3696 (19)	C11—H11B	0.9700
C4—C5	1.382 (2)	C12—O6	1.423 (2)
C5—C6	1.387 (2)	C12—H12A	0.9600
C5—H5	0.9300	C12—H12B	0.9600
C6—C7	1.511 (2)	C12—H12C	0.9600
C7—C8	1.506 (2)	N1—H1	0.8600
C7—C11	1.551 (2)	N2—O3	1.2497 (17)
C7—H7	0.9800	N2—O2	1.2613 (16)
C8—N2	1.3719 (19)	N3—O4	1.2111 (18)
C8—C9	1.401 (2)	N3—O5	1.2191 (19)
C9—N1	1.3095 (19)
C2—C1—C6	122.24 (14)	N1—C10—H10A	109.5
C2—C1—O1	115.67 (13)	N1—C10—H10B	109.5
C6—C1—O1	122.07 (13)	H10A—C10—H10B	109.5
C1—C2—C3	119.63 (14)	N1—C10—H10C	109.5
C1—C2—H2	120.2	H10A—C10—H10C	109.5
C3—C2—H2	120.2	H10B—C10—H10C	109.5
C2—C3—C4	119.43 (14)	N3—C11—C7	110.81 (12)
C2—C3—H3	120.3	N3—C11—H11A	109.5
C4—C3—H3	120.3	C7—C11—H11A	109.5
O6—C4—C5	115.20 (14)	N3—C11—H11B	109.5
O6—C4—C3	124.98 (14)	C7—C11—H11B	109.5
C5—C4—C3	119.81 (14)	H11A—C11—H11B	108.1
C6—C5—C4	121.45 (15)	O6—C12—H12A	109.5
C6—C5—H5	119.3	O6—C12—H12B	109.5
C4—C5—H5	119.3	H12A—C12—H12B	109.5
C1—C6—C5	117.41 (14)	O6—C12—H12C	109.5
C1—C6—C7	121.09 (13)	H12A—C12—H12C	109.5
C5—C6—C7	121.49 (13)	H12B—C12—H12C	109.5
C8—C7—C6	110.10 (12)	C9—N1—C10	124.87 (13)
C8—C7—C11	112.99 (13)	C9—N1—H1	117.6
C6—C7—C11	112.17 (12)	C10—N1—H1	117.6
C8—C7—H7	107.1	O3—N2—O2	120.17 (13)
C6—C7—H7	107.1	O3—N2—C8	118.59 (13)
C11—C7—H7	107.1	O2—N2—C8	121.24 (13)
N2—C8—C9	120.36 (13)	O4—N3—O5	123.00 (17)
N2—C8—C7	116.74 (13)	O4—N3—C11	118.40 (15)
C9—C8—C7	122.86 (13)	O5—N3—C11	118.53 (15)
N1—C9—O1	112.12 (13)	C9—O1—C1	120.35 (12)
N1—C9—C8	127.37 (14)	C4—O6—C12	117.96 (14)
O1—C9—C8	120.52 (13)
C6—C1—C2—C3	−1.5 (2)	N2—C8—C9—N1	7.3 (2)
O1—C1—C2—C3	177.37 (13)	C7—C8—C9—N1	−170.06 (15)
C1—C2—C3—C4	0.5 (2)	N2—C8—C9—O1	−173.30 (13)
C2—C3—C4—O6	−179.99 (14)	C7—C8—C9—O1	9.4 (2)
C2—C3—C4—C5	0.8 (2)	C8—C7—C11—N3	−55.31 (17)
O6—C4—C5—C6	179.61 (14)	C6—C7—C11—N3	69.86 (16)
C3—C4—C5—C6	−1.1 (2)	O1—C9—N1—C10	3.5 (2)
C2—C1—C6—C5	1.2 (2)	C8—C9—N1—C10	−177.05 (15)
O1—C1—C6—C5	−177.60 (13)	C9—C8—N2—O3	179.81 (14)
C2—C1—C6—C7	−178.67 (14)	C7—C8—N2—O3	−2.7 (2)
O1—C1—C6—C7	2.5 (2)	C9—C8—N2—O2	0.0 (2)
C4—C5—C6—C1	0.1 (2)	C7—C8—N2—O2	177.50 (14)
C4—C5—C6—C7	179.97 (14)	C7—C11—N3—O4	89.78 (17)
C1—C6—C7—C8	11.8 (2)	C7—C11—N3—O5	−87.28 (17)
C5—C6—C7—C8	−168.03 (14)	N1—C9—O1—C1	−173.34 (12)
C1—C6—C7—C11	−114.91 (16)	C8—C9—O1—C1	7.2 (2)
C5—C6—C7—C11	65.23 (18)	C2—C1—O1—C9	167.88 (13)
C6—C7—C8—N2	164.64 (13)	C6—C1—O1—C9	−13.3 (2)
C11—C7—C8—N2	−69.08 (17)	C5—C4—O6—C12	−178.38 (14)
C6—C7—C8—C9	−17.9 (2)	C3—C4—O6—C12	2.3 (2)
C11—C7—C8—C9	108.34 (16)

Cg is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.01	2.6169 (17)	127
N1—H1···O3i	0.86	2.26	2.9808 (18)	142
C11—H11A···O2ii	0.97	2.49	3.4366 (19)	165
C10—H10A···Cgiii	0.96	2.61	3.548 (2)	164
C10—H10C···Cgiv	0.96	2.86	3.706 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.01	2.6169 (17)	127
N1—H1⋯O3i	0.86	2.26	2.9808 (18)	142
C11—H11A⋯O2ii	0.97	2.49	3.4366 (19)	165
C10—H10A⋯Cgiii	0.96	2.61	3.548 (2)	164
C10—H10C⋯Cgiv	0.96	2.86	3.706 (2)	148

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