4-[4-(Diethyl-amino)-phen-yl]-N-methyl-3-nitro-4H-chromen-2-amine.

In the title compound, C(20)H(23)N(3)O(3), the dihydro-pyran ring adopts half-chair conformation. The chromene system makes a dihedral angle of 87.35 (5)° with the adjacent benzene ring. 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 hydrogen bonds contribute to the stabilization of the packing.

Related literature

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 ▶); Afanti­tis et al. (2006 ▶); Tang et al. (2007 ▶). For the structures of 4H-chromene derivatives, see: Muthukumaran et al. (2011 ▶); Gayathri et al. (2006 ▶); Bhaskaran et al. (2006 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H23N3O3

M = 353.41

Triclinic,

a = 8.9199 (11) Å

b = 10.4333 (12) Å

c = 11.6697 (8) Å

α = 65.100 (9)°

β = 82.388 (8)°

γ = 69.513 (11)°

V = 922.63 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.45 × 0.35 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.923, T max = 1.000

17119 measured reflections

3242 independent reflections

2625 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.162

S = 1.05

3242 reflections

226 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.44 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/S1600536811017338/sj5141sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017338/sj5141Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811017338/sj5141Isup3.cml

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

C20H23N3O3	Z = 2
Mr = 353.41	F(000) = 376
Triclinic, P1	Dx = 1.272 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9199 (11) Å	Cell parameters from 8151 reflections
b = 10.4333 (12) Å	θ = 2.7–29.3°
c = 11.6697 (8) Å	µ = 0.09 mm−1
α = 65.100 (9)°	T = 293 K
β = 82.388 (8)°	Block, yellow
γ = 69.513 (11)°	0.45 × 0.35 × 0.35 mm
V = 922.63 (19) Å3

Oxford Diffraction Xcalibur Eos diffractometer	3242 independent reflections
Radiation source: fine-focus sealed tube	2625 reflections with I > 2σ(I)
graphite	Rint = 0.036
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 = −12→12
Tmin = 0.923, Tmax = 1.000	l = −13→13
17119 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0737P)2 + 0.5254P] where P = (Fo2 + 2Fc2)/3
3242 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.52 e Å−3
3 restraints	Δρmin = −0.44 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
O1	0.42869 (17)	0.68371 (16)	0.57975 (15)	0.0483 (4)
N1	0.3634 (2)	0.9167 (2)	0.43607 (18)	0.0466 (5)
H1	0.3882	0.9910	0.3790	0.056*
N2	0.6967 (2)	0.8783 (2)	0.38082 (17)	0.0474 (5)
C8	0.6437 (2)	0.7689 (2)	0.47334 (19)	0.0395 (5)
C7	0.7689 (2)	0.6305 (2)	0.55805 (19)	0.0391 (5)
H7	0.8571	0.6001	0.5053	0.047*
O3	0.84395 (19)	0.8532 (2)	0.36670 (17)	0.0620 (5)
C9	0.4810 (2)	0.7932 (2)	0.4932 (2)	0.0397 (5)
O2	0.5993 (2)	1.00198 (19)	0.31188 (17)	0.0658 (5)
C6	0.6982 (2)	0.5058 (2)	0.6218 (2)	0.0399 (5)
C10	0.8361 (2)	0.6586 (2)	0.65559 (19)	0.0385 (5)
C15	0.9923 (2)	0.6551 (2)	0.6541 (2)	0.0425 (5)
H15	1.0599	0.6340	0.5919	0.051*
C1	0.5350 (3)	0.5370 (2)	0.6324 (2)	0.0424 (5)
C13	0.9558 (3)	0.7122 (3)	0.8384 (2)	0.0491 (6)
C5	0.7938 (3)	0.3569 (3)	0.6773 (2)	0.0484 (6)
H5	0.9044	0.3321	0.6705	0.058*
C11	0.7400 (3)	0.6897 (3)	0.7504 (2)	0.0482 (5)
H11	0.6339	0.6932	0.7536	0.058*
C14	1.0514 (3)	0.6821 (3)	0.7422 (2)	0.0478 (5)
H14	1.1570	0.6802	0.7373	0.057*
C12	0.7968 (3)	0.7153 (3)	0.8397 (2)	0.0544 (6)
H12	0.7288	0.7351	0.9022	0.065*
C20	0.1945 (3)	0.9377 (3)	0.4617 (3)	0.0563 (6)
H20A	0.1681	0.8589	0.4560	0.084*
H20B	0.1316	1.0323	0.4009	0.084*
H20C	0.1724	0.9357	0.5451	0.084*
N3	1.0125 (3)	0.7401 (3)	0.9267 (2)	0.0778 (5)
C2	0.4655 (3)	0.4275 (3)	0.6966 (2)	0.0527 (6)
H2	0.3548	0.4520	0.7021	0.063*
C3	0.5633 (3)	0.2813 (3)	0.7523 (3)	0.0602 (7)
H3	0.5187	0.2061	0.7971	0.072*
C4	0.7278 (3)	0.2458 (3)	0.7418 (2)	0.0584 (6)
H4	0.7935	0.1467	0.7784	0.070*
C18	1.1609 (4)	0.7810 (4)	0.9042 (3)	0.0778 (5)
H18A	1.1720	0.8322	0.8140	0.093*
H18B	1.1496	0.8506	0.9421	0.093*
C16	0.9352 (4)	0.7188 (4)	1.0492 (3)	0.0778 (5)
H16A	0.8790	0.6478	1.0685	0.093*
H16B	1.0165	0.6772	1.1144	0.093*
C17	0.8226 (6)	0.8584 (5)	1.0503 (5)	0.1329 (17)
H17A	0.8774	0.9296	1.0298	0.199*
H17B	0.7774	0.8405	1.1327	0.199*
H17C	0.7387	0.8971	0.9890	0.199*
C19	1.3069 (5)	0.6543 (5)	0.9545 (4)	0.1141 (14)
H19A	1.2959	0.6005	1.0433	0.171*
H19B	1.3960	0.6901	0.9411	0.171*
H19C	1.3248	0.5891	0.9120	0.171*

	U11	U22	U33	U12	U13	U23
O1	0.0341 (8)	0.0406 (8)	0.0607 (10)	−0.0087 (6)	0.0025 (7)	−0.0150 (7)
N1	0.0364 (9)	0.0393 (10)	0.0554 (11)	−0.0078 (8)	−0.0005 (8)	−0.0145 (9)
N2	0.0400 (10)	0.0525 (11)	0.0445 (11)	−0.0133 (9)	0.0030 (8)	−0.0168 (9)
C8	0.0367 (11)	0.0437 (11)	0.0381 (11)	−0.0115 (9)	0.0013 (9)	−0.0179 (9)
C7	0.0316 (10)	0.0437 (11)	0.0406 (11)	−0.0070 (8)	0.0014 (8)	−0.0202 (9)
O3	0.0406 (9)	0.0702 (11)	0.0623 (11)	−0.0191 (8)	0.0105 (8)	−0.0170 (9)
C9	0.0386 (11)	0.0401 (11)	0.0411 (11)	−0.0103 (9)	−0.0002 (9)	−0.0187 (9)
O2	0.0520 (10)	0.0530 (10)	0.0628 (11)	−0.0111 (8)	−0.0009 (8)	−0.0005 (9)
C6	0.0407 (11)	0.0436 (12)	0.0386 (11)	−0.0100 (9)	−0.0032 (9)	−0.0214 (9)
C10	0.0361 (10)	0.0386 (11)	0.0383 (11)	−0.0094 (8)	−0.0008 (8)	−0.0150 (9)
C15	0.0344 (11)	0.0470 (12)	0.0442 (12)	−0.0094 (9)	0.0013 (9)	−0.0199 (10)
C1	0.0418 (11)	0.0393 (11)	0.0451 (12)	−0.0090 (9)	−0.0023 (9)	−0.0186 (10)
C13	0.0539 (13)	0.0516 (13)	0.0449 (13)	−0.0201 (11)	−0.0051 (10)	−0.0184 (11)
C5	0.0455 (12)	0.0486 (13)	0.0494 (13)	−0.0057 (10)	−0.0061 (10)	−0.0241 (11)
C11	0.0381 (11)	0.0626 (14)	0.0517 (13)	−0.0198 (10)	0.0060 (10)	−0.0292 (11)
C14	0.0371 (11)	0.0543 (13)	0.0515 (13)	−0.0157 (10)	−0.0025 (10)	−0.0192 (11)
C12	0.0543 (14)	0.0726 (16)	0.0496 (14)	−0.0261 (12)	0.0123 (11)	−0.0359 (13)
C20	0.0363 (12)	0.0499 (13)	0.0732 (17)	−0.0054 (10)	0.0002 (11)	−0.0229 (12)
N3	0.0905 (12)	0.1014 (13)	0.0670 (10)	−0.0482 (10)	−0.0023 (9)	−0.0428 (10)
C2	0.0494 (13)	0.0516 (14)	0.0595 (15)	−0.0204 (11)	0.0012 (11)	−0.0216 (12)
C3	0.0729 (17)	0.0459 (14)	0.0617 (16)	−0.0251 (12)	−0.0033 (13)	−0.0158 (12)
C4	0.0681 (17)	0.0405 (13)	0.0597 (15)	−0.0073 (11)	−0.0104 (12)	−0.0191 (11)
C18	0.0905 (12)	0.1014 (13)	0.0670 (10)	−0.0482 (10)	−0.0023 (9)	−0.0428 (10)
C16	0.0905 (12)	0.1014 (13)	0.0670 (10)	−0.0482 (10)	−0.0023 (9)	−0.0428 (10)
C17	0.172 (5)	0.129 (4)	0.145 (4)	−0.071 (3)	0.028 (3)	−0.088 (3)
C19	0.094 (3)	0.151 (4)	0.098 (3)	−0.039 (3)	−0.022 (2)	−0.044 (3)

O1—C9	1.349 (3)	C11—C12	1.373 (3)
O1—C1	1.402 (2)	C11—H11	0.9300
N1—C9	1.312 (3)	C14—H14	0.9300
N1—C20	1.453 (3)	C12—H12	0.9300
N1—H1	0.8600	C20—H20A	0.9600
N2—O3	1.249 (2)	C20—H20B	0.9600
N2—O2	1.262 (2)	C20—H20C	0.9600
N2—C8	1.377 (3)	N3—C16	1.465 (4)
C8—C9	1.388 (3)	N3—C18	1.487 (4)
C8—C7	1.507 (3)	C2—C3	1.376 (3)
C7—C6	1.510 (3)	C2—H2	0.9300
C7—C10	1.525 (3)	C3—C4	1.384 (4)
C7—H7	0.9800	C3—H3	0.9300
O3—N2	1.249 (2)	C4—H4	0.9300
O2—N2	1.262 (2)	C18—C19	1.460 (5)
C6—C1	1.377 (3)	C18—H18A	0.9700
C6—C5	1.390 (3)	C18—H18B	0.9700
C10—C15	1.380 (3)	C16—C17	1.455 (5)
C10—C11	1.385 (3)	C16—H16A	0.9700
C15—C14	1.380 (3)	C16—H16B	0.9700
C15—H15	0.9300	C17—H17A	0.9600
C1—C2	1.380 (3)	C17—H17B	0.9600
C13—N3	1.378 (3)	C17—H17C	0.9600
C13—C14	1.393 (3)	C19—H19A	0.9600
C13—C12	1.406 (3)	C19—H19B	0.9600
C5—C4	1.372 (4)	C19—H19C	0.9600
C5—H5	0.9300
C9—O1—C1	119.79 (16)	C11—C12—H12	119.4
C9—N1—C20	125.1 (2)	C13—C12—H12	119.4
C9—N1—H1	117.5	N1—C20—H20A	109.5
C20—N1—H1	117.5	N1—C20—H20B	109.5
O3—N2—O2	120.32 (18)	H20A—C20—H20B	109.5
O3—N2—O2	120.32 (18)	N1—C20—H20C	109.5
O3—N2—C8	118.58 (18)	H20A—C20—H20C	109.5
O2—N2—C8	121.10 (18)	H20B—C20—H20C	109.5
N2—C8—C9	120.35 (19)	C13—N3—C16	120.7 (2)
N2—C8—C7	117.15 (17)	C13—N3—C18	120.8 (2)
C9—C8—C7	122.25 (19)	C16—N3—C18	118.3 (2)
C6—C7—C8	109.37 (17)	C3—C2—C1	118.6 (2)
C6—C7—C10	110.83 (17)	C3—C2—H2	120.7
C8—C7—C10	111.95 (17)	C1—C2—H2	120.7
C6—C7—H7	108.2	C2—C3—C4	120.2 (2)
C10—C7—H7	108.2	C2—C3—H3	119.9
N1—C9—O1	112.50 (18)	C4—C3—H3	119.9
N1—C9—C8	127.1 (2)	C5—C4—C3	119.9 (2)
O1—C9—C8	120.41 (18)	C5—C4—H4	120.0
C1—C6—C5	117.4 (2)	C3—C4—H4	120.0
C1—C6—C7	120.57 (18)	C19—C18—N3	114.4 (3)
C5—C6—C7	121.92 (19)	C19—C18—H18A	108.7
C15—C10—C11	117.06 (19)	N3—C18—H18A	108.7
C15—C10—C7	122.49 (18)	C19—C18—H18B	108.7
C11—C10—C7	120.45 (18)	N3—C18—H18B	108.7
C14—C15—C10	122.0 (2)	H18A—C18—H18B	107.6
C14—C15—H15	119.0	C17—C16—N3	112.0 (3)
C10—C15—H15	119.0	C17—C16—H16A	109.2
C6—C1—C2	122.6 (2)	N3—C16—H16A	109.2
C6—C1—O1	121.69 (19)	C17—C16—H16B	109.2
C2—C1—O1	115.70 (19)	N3—C16—H16B	109.2
N3—C13—C14	122.1 (2)	H16A—C16—H16B	107.9
N3—C13—C12	121.4 (2)	C16—C17—H17A	109.5
C14—C13—C12	116.5 (2)	C16—C17—H17B	109.5
C4—C5—C6	121.2 (2)	H17A—C17—H17B	109.5
C4—C5—H5	119.4	C16—C17—H17C	109.5
C6—C5—H5	119.4	H17A—C17—H17C	109.5
C12—C11—C10	121.9 (2)	H17B—C17—H17C	109.5
C12—C11—H11	119.0	C18—C19—H19A	109.5
C10—C11—H11	119.0	C18—C19—H19B	109.5
C15—C14—C13	121.3 (2)	H19A—C19—H19B	109.5
C15—C14—H14	119.3	C18—C19—H19C	109.5
C13—C14—H14	119.3	H19A—C19—H19C	109.5
C11—C12—C13	121.2 (2)	H19B—C19—H19C	109.5
O3—N2—C8—N2	0(17)	C8—C7—C6—C5	162.23 (19)
O2—N2—C8—N2	0(100)	C10—C7—C6—C5	−73.9 (2)
O2—N2—C8—N2	0(100)	C6—C7—C10—C15	124.8 (2)
N2—N2—C8—C9	0.00 (11)	C8—C7—C10—C15	−112.8 (2)
O3—N2—C8—C9	179.15 (19)	C6—C7—C10—C11	−55.4 (3)
O2—N2—C8—C9	−0.4 (3)	C8—C7—C10—C11	67.0 (3)
O2—N2—C8—C9	−0.4 (3)	C11—C10—C15—C14	−0.4 (3)
N2—N2—C8—C7	0.00 (19)	C7—C10—C15—C14	179.4 (2)
O3—N2—C8—C7	4.7 (3)	C5—C6—C1—C2	1.0 (3)
O2—N2—C8—C7	−174.88 (19)	C7—C6—C1—C2	−175.9 (2)
O2—N2—C8—C7	−174.88 (19)	C5—C6—C1—O1	179.92 (18)
N2—C8—C7—C6	−161.30 (17)	C7—C6—C1—O1	3.0 (3)
N2—C8—C7—C6	−161.30 (17)	C9—O1—C1—C6	15.4 (3)
C9—C8—C7—C6	24.4 (3)	C9—O1—C1—C2	−165.57 (19)
N2—C8—C7—C10	75.5 (2)	C1—C6—C5—C4	−1.0 (3)
N2—C8—C7—C10	75.5 (2)	C7—C6—C5—C4	175.8 (2)
C9—C8—C7—C10	−98.9 (2)	C15—C10—C11—C12	−0.3 (3)
O2—N2—O3—N2	0(39)	C7—C10—C11—C12	179.9 (2)
O2—N2—O3—N2	0(39)	C10—C15—C14—C13	1.0 (3)
C8—N2—O3—N2	0(100)	N3—C13—C14—C15	−179.6 (2)
C20—N1—C9—O1	0.6 (3)	C12—C13—C14—C15	−0.8 (3)
C20—N1—C9—C8	−178.9 (2)	C10—C11—C12—C13	0.4 (4)
C1—O1—C9—N1	168.16 (18)	N3—C13—C12—C11	179.0 (2)
C1—O1—C9—C8	−12.3 (3)	C14—C13—C12—C11	0.1 (4)
N2—C8—C9—N1	−3.7 (3)	C14—C13—N3—C16	−158.1 (3)
N2—C8—C9—N1	−3.7 (3)	C12—C13—N3—C16	23.1 (4)
C7—C8—C9—N1	170.5 (2)	C14—C13—N3—C18	17.1 (4)
N2—C8—C9—O1	176.92 (18)	C12—C13—N3—C18	−161.7 (3)
N2—C8—C9—O1	176.92 (18)	C6—C1—C2—C3	0.0 (4)
C7—C8—C9—O1	−8.9 (3)	O1—C1—C2—C3	−179.0 (2)
N2—N2—O2—O2	0.0	C1—C2—C3—C4	−1.0 (4)
O3—N2—O2—O2	0.0 (2)	C6—C5—C4—C3	0.1 (4)
C8—N2—O2—O2	0.00 (11)	C2—C3—C4—C5	1.0 (4)
O3—N2—O2—N2	0(10)	C13—N3—C18—C19	−92.4 (4)
O2—N2—O2—N2	0(100)	C16—N3—C18—C19	82.9 (4)
C8—N2—O2—N2	0(100)	C13—N3—C16—C17	−97.1 (4)
C8—C7—C6—C1	−21.0 (3)	C18—N3—C16—C17	87.6 (4)
C10—C7—C6—C1	102.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.96	2.596 (2)	129
C5—H5···O3i	0.93	2.52	3.325 (3)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.96	2.596 (2)	129
C5—H5⋯O3i	0.93	2.52	3.325 (3)	144

Symmetry code: (i) .