6,8-Dichloro-N-methyl-3-nitro-4-nitro-methyl-4H-chromen-2-amine.

In the title compound, C(11)H(9)Cl(2)N(3)O(5), the dihydro-pyran ring adopts a near-half-chair conformation. The benzene ring makes a torsion angle of 5.02 (5)° with the dihydro-pyran ring. Adjacent mol-ecules are inter-linked through inter-molecular C-H⋯O, N-H⋯O and C-Cl⋯π [3.4743 (9) Å] inter-actions. The inter-molecular N-H⋯O hydrogen bond generates an R(2) (2)(12) motif, which is observed to contribute to the crystal packing stability. Moreover, the mol-ecular structure displays an S(6) motif formed by intra-molecular N-H⋯O hydrogen bonding.

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 (1988 ▶); Brooks (1998 ▶); Valenti et al. (1993 ▶); Hyana & Saimoto (1987 ▶); Tang et al. (2007 ▶). For ring-puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C11H9Cl2N3O5

M = 334.11

Triclinic,

a = 8.7426 (7) Å

b = 9.2727 (7) Å

c = 9.3420 (7) Å

α = 70.017 (7)°

β = 72.609 (7)°

γ = 87.579 (6)°

V = 677.68 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.50 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 = 0.792, T max = 1.000

15150 measured reflections

2385 independent reflections

2072 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.110

S = 1.01

2385 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.30 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/S1600536811009366/zq2089sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009366/zq2089Isup2.hkl

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

C11H9Cl2N3O5	Z = 2
Mr = 334.11	F(000) = 340
Triclinic, P1	Dx = 1.637 Mg m−3
Hall symbol: -P 1	Melting point: 485.65 K
a = 8.7426 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2727 (7) Å	Cell parameters from 8735 reflections
c = 9.3420 (7) Å	θ = 2.7–29.2°
α = 70.017 (7)°	µ = 0.50 mm−1
β = 72.609 (7)°	T = 293 K
γ = 87.579 (6)°	Block, colourless
V = 677.68 (9) Å3	0.4 × 0.35 × 0.2 mm

Oxford Diffraction Xcalibur Eos diffractometer	2385 independent reflections
Radiation source: fine-focus sealed tube	2072 reflections with I > 2σ(I)
graphite	Rint = 0.034
Detector resolution: 15.9821 pixels mm-1	θmax = 25.0°, θmin = 2.7°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→11
Tmin = 0.792, Tmax = 1.000	l = −11→11
15150 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.091P)2] where P = (Fo2 + 2Fc2)/3
2385 reflections	(Δ/σ)max = 0.046
191 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.30 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
Cl1	0.66030 (6)	0.29149 (5)	−0.00059 (6)	0.04277 (19)
Cl2	0.68824 (8)	0.83939 (6)	−0.46350 (6)	0.0599 (2)
O1	0.77375 (15)	0.46548 (12)	0.15081 (14)	0.0344 (3)
C6	0.79885 (19)	0.71693 (18)	−0.05514 (19)	0.0273 (4)
O3	1.02216 (15)	0.86894 (13)	0.20553 (15)	0.0389 (3)
N2	0.98248 (17)	0.72806 (15)	0.25417 (16)	0.0321 (3)
O2	1.01949 (18)	0.63676 (15)	0.37199 (16)	0.0494 (4)
O4	0.55005 (17)	0.69199 (16)	0.26437 (17)	0.0502 (4)
C1	0.7612 (2)	0.55977 (18)	0.00458 (19)	0.0283 (4)
C5	0.7793 (2)	0.80191 (19)	−0.20214 (19)	0.0312 (4)
H5	0.8046	0.9075	−0.2450	0.037*
C7	0.8539 (2)	0.79260 (17)	0.04217 (19)	0.0275 (4)
H7	0.9526	0.8554	−0.0288	0.033*
N1	0.8653 (2)	0.40896 (17)	0.35814 (18)	0.0383 (4)
H1	0.9139	0.4331	0.4152	0.046*
C3	0.6865 (2)	0.5726 (2)	−0.2272 (2)	0.0365 (4)
H3	0.6498	0.5253	−0.2850	0.044*
C8	0.8987 (2)	0.67447 (18)	0.17785 (19)	0.0285 (4)
C2	0.7067 (2)	0.48781 (19)	−0.0813 (2)	0.0316 (4)
C9	0.8488 (2)	0.51877 (19)	0.23183 (19)	0.0298 (4)
N3	0.56967 (19)	0.83127 (18)	0.19612 (18)	0.0373 (4)
C11	0.7329 (2)	0.90325 (17)	0.0935 (2)	0.0326 (4)
H11A	0.7759	0.9524	0.1510	0.039*
H11B	0.7223	0.9831	−0.0017	0.039*
C4	0.7221 (2)	0.7293 (2)	−0.2847 (2)	0.0355 (4)
C10	0.8075 (3)	0.2491 (2)	0.4088 (3)	0.0485 (5)
H10A	0.8584	0.2078	0.3263	0.073*
H10B	0.6932	0.2433	0.4287	0.073*
H10C	0.8325	0.1909	0.5049	0.073*
O5	0.4625 (2)	0.9172 (2)	0.2075 (2)	0.0744 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0508 (3)	0.0246 (3)	0.0566 (3)	−0.0001 (2)	−0.0175 (2)	−0.0172 (2)
Cl2	0.0942 (5)	0.0534 (4)	0.0365 (3)	0.0011 (3)	−0.0335 (3)	−0.0086 (2)
O1	0.0450 (7)	0.0202 (6)	0.0367 (6)	−0.0035 (5)	−0.0182 (5)	−0.0025 (5)
C6	0.0271 (8)	0.0246 (8)	0.0290 (8)	0.0025 (6)	−0.0077 (6)	−0.0084 (6)
O3	0.0469 (8)	0.0250 (7)	0.0444 (7)	−0.0074 (5)	−0.0186 (6)	−0.0064 (5)
N2	0.0362 (8)	0.0250 (8)	0.0314 (7)	−0.0018 (6)	−0.0139 (6)	−0.0018 (6)
O2	0.0678 (10)	0.0365 (8)	0.0478 (8)	−0.0027 (7)	−0.0388 (7)	−0.0004 (6)
O4	0.0407 (8)	0.0409 (8)	0.0602 (9)	−0.0049 (6)	−0.0082 (7)	−0.0117 (7)
C1	0.0295 (9)	0.0229 (8)	0.0299 (8)	0.0040 (6)	−0.0083 (7)	−0.0068 (6)
C5	0.0348 (9)	0.0245 (9)	0.0293 (8)	0.0015 (7)	−0.0071 (7)	−0.0053 (7)
C7	0.0308 (9)	0.0186 (8)	0.0295 (8)	−0.0006 (6)	−0.0096 (7)	−0.0030 (6)
N1	0.0483 (9)	0.0252 (8)	0.0387 (8)	−0.0021 (6)	−0.0221 (7)	0.0006 (6)
C3	0.0392 (10)	0.0387 (11)	0.0383 (10)	0.0041 (8)	−0.0126 (8)	−0.0208 (8)
C8	0.0309 (9)	0.0229 (8)	0.0307 (8)	0.0002 (7)	−0.0130 (7)	−0.0044 (6)
C2	0.0309 (9)	0.0238 (9)	0.0401 (9)	0.0028 (7)	−0.0077 (7)	−0.0136 (7)
C9	0.0296 (9)	0.0248 (9)	0.0322 (9)	0.0021 (7)	−0.0109 (7)	−0.0050 (7)
N3	0.0405 (9)	0.0388 (9)	0.0378 (8)	0.0085 (7)	−0.0150 (7)	−0.0177 (7)
C11	0.0397 (10)	0.0210 (8)	0.0383 (9)	0.0022 (7)	−0.0163 (7)	−0.0078 (7)
C4	0.0409 (10)	0.0369 (10)	0.0277 (8)	0.0045 (8)	−0.0101 (7)	−0.0106 (7)
C10	0.0579 (13)	0.0245 (10)	0.0514 (11)	−0.0055 (9)	−0.0192 (10)	0.0047 (8)
O5	0.0539 (10)	0.0656 (11)	0.0901 (13)	0.0263 (9)	−0.0061 (9)	−0.0262 (9)

Cl1—C2	1.7287 (16)	C7—H7	0.9800
Cl2—C4	1.7391 (17)	N1—C9	1.311 (2)
O1—C9	1.352 (2)	N1—C10	1.455 (2)
O1—C1	1.3812 (19)	N1—H1	0.8600
C6—C1	1.385 (2)	C3—C2	1.381 (2)
C6—C5	1.388 (2)	C3—C4	1.379 (2)
C6—C7	1.509 (2)	C3—H3	0.9300
O3—N2	1.2537 (17)	C8—C9	1.398 (2)
N2—O2	1.2593 (18)	N3—O5	1.208 (2)
N2—C8	1.370 (2)	N3—C11	1.492 (2)
O4—N3	1.222 (2)	C11—H11A	0.9700
C1—C2	1.392 (2)	C11—H11B	0.9700
C5—C4	1.383 (2)	C10—H10A	0.9600
C5—H5	0.9300	C10—H10B	0.9600
C7—C8	1.507 (2)	C10—H10C	0.9600
C7—C11	1.531 (2)
C9—O1—C1	120.56 (13)	N2—C8—C7	116.78 (13)
C1—C6—C5	118.53 (15)	C9—C8—C7	122.28 (14)
C1—C6—C7	119.89 (14)	C3—C2—C1	120.45 (15)
C5—C6—C7	121.54 (14)	C3—C2—Cl1	120.48 (13)
O3—N2—O2	120.24 (13)	C1—C2—Cl1	119.04 (13)
O3—N2—C8	119.38 (12)	N1—C9—O1	111.86 (15)
O2—N2—C8	120.38 (13)	N1—C9—C8	127.76 (16)
O1—C1—C6	123.02 (14)	O1—C9—C8	120.38 (14)
O1—C1—C2	116.01 (14)	O5—N3—O4	123.38 (17)
C6—C1—C2	120.97 (15)	O5—N3—C11	116.64 (16)
C4—C5—C6	119.86 (15)	O4—N3—C11	119.98 (14)
C4—C5—H5	120.1	N3—C11—C7	115.17 (13)
C6—C5—H5	120.1	N3—C11—H11A	108.5
C8—C7—C6	110.98 (13)	C7—C11—H11A	108.5
C8—C7—C11	114.16 (13)	N3—C11—H11B	108.5
C6—C7—C11	111.64 (13)	C7—C11—H11B	108.5
C8—C7—H7	106.5	H11A—C11—H11B	107.5
C6—C7—H7	106.5	C3—C4—C5	121.98 (15)
C11—C7—H7	106.5	C3—C4—Cl2	118.91 (13)
C9—N1—C10	124.73 (17)	C5—C4—Cl2	119.08 (13)
C9—N1—H1	117.6	N1—C10—H10A	109.5
C10—N1—H1	117.6	N1—C10—H10B	109.5
C2—C3—C4	118.19 (15)	H10A—C10—H10B	109.5
C2—C3—H3	120.9	N1—C10—H10C	109.5
C4—C3—H3	120.9	H10A—C10—H10C	109.5
N2—C8—C9	120.80 (14)	H10B—C10—H10C	109.5
C9—O1—C1—C6	−10.9 (2)	C4—C3—C2—Cl1	178.69 (13)
C9—O1—C1—C2	169.50 (14)	O1—C1—C2—C3	178.49 (15)
C5—C6—C1—O1	−178.84 (15)	C6—C1—C2—C3	−1.1 (2)
C7—C6—C1—O1	−1.1 (2)	O1—C1—C2—Cl1	0.0 (2)
C5—C6—C1—C2	0.8 (2)	C6—C1—C2—Cl1	−179.62 (13)
C7—C6—C1—C2	178.55 (15)	C10—N1—C9—O1	−1.3 (3)
C1—C6—C5—C4	0.5 (2)	C10—N1—C9—C8	178.82 (18)
C7—C6—C5—C4	−177.25 (15)	C1—O1—C9—N1	−172.63 (14)
C1—C6—C7—C8	14.2 (2)	C1—O1—C9—C8	7.2 (2)
C5—C6—C7—C8	−168.08 (15)	N2—C8—C9—N1	3.4 (3)
C1—C6—C7—C11	−114.39 (16)	C7—C8—C9—N1	−172.13 (17)
C5—C6—C7—C11	63.3 (2)	N2—C8—C9—O1	−176.45 (15)
O3—N2—C8—C9	−178.20 (15)	C7—C8—C9—O1	8.0 (2)
O2—N2—C8—C9	1.9 (2)	O5—N3—C11—C7	−163.02 (15)
O3—N2—C8—C7	−2.4 (2)	O4—N3—C11—C7	17.5 (2)
O2—N2—C8—C7	177.65 (15)	C8—C7—C11—N3	−65.94 (19)
C6—C7—C8—N2	166.39 (14)	C6—C7—C11—N3	60.95 (17)
C11—C7—C8—N2	−66.4 (2)	C2—C3—C4—C5	1.1 (3)
C6—C7—C8—C9	−17.9 (2)	C2—C3—C4—Cl2	−176.92 (14)
C11—C7—C8—C9	109.33 (17)	C6—C5—C4—C3	−1.4 (3)
C4—C3—C2—C1	0.2 (3)	C6—C5—C4—Cl2	176.55 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.00	2.613 (2)	128
N1—H1···O2i	0.86	2.12	2.881 (2)	147
C7—H7···O3ii	0.98	2.50	3.1944 (19)	128
C11—H11B···O3ii	0.97	2.54	3.103 (2)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.00	2.613 (2)	128
N1—H1⋯O2i	0.86	2.12	2.881 (2)	147
C7—H7⋯O3ii	0.98	2.50	3.1944 (19)	128
C11—H11B⋯O3ii	0.97	2.54	3.103 (2)	117

Symmetry codes: (i) ; (ii) .