3-Nitro-2-phenyl­chroman

Abstract

In the title compound, C₁₅H₁₃NO₃, the dihedral angle between the two aromatic rings is 79.25 (16)°.

Related literature  

For pharmaceutical and synthetic applications of compounds with a benzopyran framework, see: Horton et al. (2003 ▶); Murugesh et al. (1996 ▶); Engler et al. (1990 ▶).

Experimental  

Crystal data  

• C₁₅H₁₃NO₃

• M _r = 255.26

• Triclinic,

• a = 5.3769 (11) Å

• b = 10.105 (2) Å

• c = 12.320 (3) Å

• α = 70.85 (3)°

• β = 82.89 (3)°

• γ = 84.87 (3)°

• V = 626.6 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.20 × 0.20 × 0.10 mm

Data collection  

• Rigaku Saturn diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.981, T _max = 0.991

• 5249 measured reflections

• 2205 independent reflections

• 912 reflections with I > 2σ(I)

• R _int = 0.053

Refinement  

• R[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 0.152

• S = 1.07

• 2205 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.47 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812020806/tk5093Isup3.cml

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

supplementary crystallographic information

Comment

Compounds containing a benzopyran framework have anti-tumour, anti-bacterial and anti-inflammatory activities (Horton et al., 2003). Additionally, they are also useful intermediates in the synthesis of complex natural products (Engler et al.,1990; Murugesh et al., 1996). The title compound, a member of this class of compounds, was synthesised and characterised by X-ray crystallography.

As shown in Fig. 1, the crystal structure determination indicates that the dihedral angle between the two aromatic rings is 79.25 (16)°.

Experimental

2-Phenyl-1-nitroethane (10.5 mmol), dimethyl amine hydrochloride (20 mmol), benzaldehyde (10.5 mmol), toluene (7.5 ml) and potassium fluoride (0.08 mmol) were taken in a 50 ml round bottomed flask fitted with a Dean-Stark water separator. The mixture was refluxed with stirring for 10 h. The solvent was removed from the reaction vessel to give a crude product. Chloroform (5 ml) and 0.2 M HCl (10 ml) were added to the crude material and the solution was heated on a water bath at 60 °C for 2 min under reduced pressure. The mixture was extracted with dichloroform. The organic extracts were dried over anhydrous magnesium sulfate. The residue was chromatographed on silica gel by eluting with EtOAc/pet. ether to give the desired product. Crystals of the title compound were obtained by slow evaporation of its dichloromethane/n-hexane solution at room temperature. ¹N NMR (400 MHz, CDCl₃, TMS): 7.43 (s, 5H), 7.24 (m, 2H), 7.02 (m, 2H), 5.45 (d, 1H, J = 8.0 Hz), 5.08 (m, 1H), 3.69 (dd, 1H, J = 9.2, 16.0 Hz), 3.35 (dd, 1H, J = 9.2, 16.0 Hz) p.p.m.. ¹³C NMR (100.6 MHz, CDCl₃, TMS): 153.3, 135.8, 129.5, 129.4, 129.0, 128.5, 126.9, 122.0, 117.7, 117.0, 84.0, 78.0, 29.8 p.p.m..

Refinement

The H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Crystal data

C15H13NO3	Z = 2
Mr = 255.26	F(000) = 268
Triclinic, P1	Dx = 1.353 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3769 (11) Å	Cell parameters from 1554 reflections
b = 10.105 (2) Å	θ = 3.5–28.0°
c = 12.320 (3) Å	µ = 0.10 mm−1
α = 70.85 (3)°	T = 293 K
β = 82.89 (3)°	Prism, colourless
γ = 84.87 (3)°	0.20 × 0.20 × 0.10 mm
V = 626.6 (2) Å3

Data collection

Rigaku Saturn diffractometer	2205 independent reflections
Radiation source: rotating anode	912 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.053
ω scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −6→6
Tmin = 0.981, Tmax = 0.991	k = −11→10
5249 measured reflections	l = −14→14

Refinement

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0551P)2] where P = (Fo2 + 2Fc2)/3
2205 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1296 (3)	0.85831 (18)	0.15383 (15)	0.0443 (5)
O2	0.6208 (5)	0.6744 (3)	0.4385 (2)	0.0835 (8)
O3	0.2445 (5)	0.6648 (3)	0.5113 (2)	0.0841 (9)
N1	0.4007 (6)	0.6773 (2)	0.4307 (2)	0.0491 (7)
C1	0.0165 (5)	0.7495 (3)	0.1373 (2)	0.0399 (7)
C2	−0.1198 (6)	0.7845 (3)	0.0429 (2)	0.0512 (8)
H2	−0.1301	0.8766	−0.0060	0.061*
C3	−0.2397 (6)	0.6827 (4)	0.0218 (3)	0.0644 (10)
H3	−0.3332	0.7058	−0.0412	0.077*
C4	−0.2215 (7)	0.5453 (3)	0.0943 (3)	0.0667 (10)
H4	−0.3032	0.4759	0.0805	0.080*
C5	−0.0821 (6)	0.5123 (3)	0.1865 (3)	0.0542 (9)
H5	−0.0692	0.4197	0.2344	0.065*
C6	0.0406 (5)	0.6137 (3)	0.2101 (2)	0.0401 (7)
C7	0.1895 (5)	0.5749 (3)	0.3130 (2)	0.0456 (8)
H7A	0.0780	0.5414	0.3834	0.055*
H7B	0.3127	0.4998	0.3097	0.055*
C8	0.3187 (7)	0.6980 (3)	0.3148 (3)	0.0594 (9)
H8	0.4734	0.7018	0.2629	0.071*
C9	0.1824 (7)	0.8331 (3)	0.2685 (3)	0.0637 (10)
H9	0.0198	0.8268	0.3151	0.076*
C10	0.3006 (6)	0.9590 (3)	0.2757 (3)	0.0467 (8)
C11	0.1942 (6)	1.0227 (3)	0.3531 (3)	0.0658 (10)
H11	0.0462	0.9899	0.3978	0.079*
C12	0.3002 (8)	1.1345 (4)	0.3669 (3)	0.0782 (12)
H12	0.2248	1.1764	0.4205	0.094*
C13	0.5127 (7)	1.1822 (3)	0.3026 (3)	0.0679 (11)
H13	0.5866	1.2567	0.3125	0.081*
C14	0.6212 (6)	1.1230 (4)	0.2231 (3)	0.0676 (10)
H14	0.7674	1.1577	0.1778	0.081*
C15	0.5138 (7)	1.0110 (3)	0.2099 (3)	0.0606 (9)
H15	0.5882	0.9706	0.1552	0.073*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0569 (13)	0.0382 (11)	0.0365 (11)	−0.0084 (10)	−0.0131 (10)	−0.0056 (9)
O2	0.0496 (16)	0.101 (2)	0.094 (2)	0.0026 (13)	−0.0252 (15)	−0.0196 (15)
O3	0.094 (2)	0.103 (2)	0.0542 (15)	−0.0355 (16)	0.0116 (15)	−0.0226 (14)
N1	0.0566 (19)	0.0415 (15)	0.0463 (17)	−0.0090 (13)	−0.0147 (15)	−0.0052 (12)
C1	0.0473 (18)	0.0380 (17)	0.0373 (17)	−0.0044 (14)	−0.0070 (14)	−0.0143 (14)
C2	0.070 (2)	0.0444 (17)	0.0413 (18)	−0.0029 (16)	−0.0167 (16)	−0.0128 (15)
C3	0.083 (3)	0.066 (2)	0.052 (2)	−0.006 (2)	−0.0293 (19)	−0.0204 (19)
C4	0.087 (3)	0.058 (2)	0.069 (2)	−0.0154 (19)	−0.028 (2)	−0.0283 (19)
C5	0.067 (2)	0.0424 (18)	0.053 (2)	−0.0135 (16)	−0.0101 (18)	−0.0110 (15)
C6	0.0431 (18)	0.0395 (16)	0.0384 (17)	−0.0048 (14)	−0.0057 (14)	−0.0120 (14)
C7	0.0541 (19)	0.0345 (16)	0.0472 (18)	−0.0075 (14)	−0.0133 (15)	−0.0074 (14)
C8	0.084 (3)	0.048 (2)	0.049 (2)	−0.0038 (18)	−0.0345 (18)	−0.0092 (16)
C9	0.097 (3)	0.045 (2)	0.051 (2)	−0.0102 (19)	−0.032 (2)	−0.0076 (16)
C10	0.060 (2)	0.0340 (16)	0.0442 (18)	−0.0099 (16)	−0.0170 (17)	−0.0037 (14)
C11	0.061 (2)	0.065 (2)	0.070 (2)	−0.0217 (19)	0.008 (2)	−0.019 (2)
C12	0.106 (3)	0.064 (2)	0.072 (3)	−0.022 (2)	0.012 (2)	−0.034 (2)
C13	0.082 (3)	0.056 (2)	0.071 (2)	−0.027 (2)	−0.018 (2)	−0.018 (2)
C14	0.046 (2)	0.068 (2)	0.081 (3)	−0.0128 (19)	−0.003 (2)	−0.013 (2)
C15	0.074 (3)	0.049 (2)	0.060 (2)	0.0029 (19)	−0.003 (2)	−0.0217 (17)

Geometric parameters (Å, º)

O1—C1	1.385 (3)	C7—H7A	0.9700
O1—C9	1.411 (3)	C7—H7B	0.9700
O2—N1	1.196 (3)	C8—C9	1.463 (4)
O3—N1	1.199 (3)	C8—H8	0.9800
N1—C8	1.490 (3)	C9—C10	1.505 (4)
C1—C6	1.376 (4)	C9—H9	0.9800
C1—C2	1.381 (4)	C10—C15	1.359 (4)
C2—C3	1.370 (4)	C10—C11	1.361 (4)
C2—H2	0.9300	C11—C12	1.376 (4)
C3—C4	1.385 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.338 (5)
C4—C5	1.371 (4)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.356 (5)
C5—C6	1.391 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.379 (4)
C6—C7	1.507 (4)	C14—H14	0.9300
C7—C8	1.486 (4)	C15—H15	0.9300
C1—O1—C9	114.2 (2)	C9—C8—N1	112.6 (3)
O2—N1—O3	123.1 (3)	C7—C8—N1	111.7 (2)
O2—N1—C8	118.0 (3)	C9—C8—H8	105.7
O3—N1—C8	118.9 (3)	C7—C8—H8	105.7
C6—C1—C2	121.8 (3)	N1—C8—H8	105.7
C6—C1—O1	121.8 (2)	O1—C9—C8	112.2 (2)
C2—C1—O1	116.3 (3)	O1—C9—C10	109.2 (2)
C3—C2—C1	119.7 (3)	C8—C9—C10	116.0 (3)
C3—C2—H2	120.2	O1—C9—H9	106.3
C1—C2—H2	120.2	C8—C9—H9	106.3
C2—C3—C4	119.9 (3)	C10—C9—H9	106.3
C2—C3—H3	120.1	C15—C10—C11	117.9 (3)
C4—C3—H3	120.1	C15—C10—C9	122.9 (3)
C5—C4—C3	119.6 (3)	C11—C10—C9	119.2 (3)
C5—C4—H4	120.2	C10—C11—C12	121.6 (3)
C3—C4—H4	120.2	C10—C11—H11	119.2
C4—C5—C6	121.7 (3)	C12—C11—H11	119.2
C4—C5—H5	119.2	C13—C12—C11	119.4 (3)
C6—C5—H5	119.2	C13—C12—H12	120.3
C1—C6—C5	117.4 (3)	C11—C12—H12	120.3
C1—C6—C7	122.1 (2)	C12—C13—C14	120.6 (3)
C5—C6—C7	120.6 (3)	C12—C13—H13	119.7
C8—C7—C6	110.6 (2)	C14—C13—H13	119.7
C8—C7—H7A	109.5	C13—C14—C15	119.7 (3)
C6—C7—H7A	109.5	C13—C14—H14	120.2
C8—C7—H7B	109.5	C15—C14—H14	120.2
C6—C7—H7B	109.5	C10—C15—C14	120.8 (3)
H7A—C7—H7B	108.1	C10—C15—H15	119.6
C9—C8—C7	114.6 (3)	C14—C15—H15	119.6
C9—O1—C1—C6	−23.5 (4)	O3—N1—C8—C7	−63.3 (4)
C9—O1—C1—C2	157.1 (3)	C1—O1—C9—C8	50.9 (4)
C6—C1—C2—C3	1.4 (4)	C1—O1—C9—C10	−179.1 (2)
O1—C1—C2—C3	−179.2 (3)	C7—C8—C9—O1	−57.3 (4)
C1—C2—C3—C4	−0.7 (5)	N1—C8—C9—O1	173.5 (3)
C2—C3—C4—C5	−0.3 (5)	C7—C8—C9—C10	176.4 (3)
C3—C4—C5—C6	0.6 (5)	N1—C8—C9—C10	47.2 (4)
C2—C1—C6—C5	−1.1 (4)	O1—C9—C10—C15	−57.1 (4)
O1—C1—C6—C5	179.5 (2)	C8—C9—C10—C15	70.7 (4)
C2—C1—C6—C7	179.9 (3)	O1—C9—C10—C11	124.4 (3)
O1—C1—C6—C7	0.5 (4)	C8—C9—C10—C11	−107.8 (4)
C4—C5—C6—C1	0.1 (4)	C15—C10—C11—C12	−1.4 (5)
C4—C5—C6—C7	179.1 (3)	C9—C10—C11—C12	177.2 (3)
C1—C6—C7—C8	−5.5 (4)	C10—C11—C12—C13	0.2 (6)
C5—C6—C7—C8	175.5 (3)	C11—C12—C13—C14	1.1 (6)
C6—C7—C8—C9	32.9 (4)	C12—C13—C14—C15	−1.1 (6)
C6—C7—C8—N1	162.5 (3)	C11—C10—C15—C14	1.4 (5)
O2—N1—C8—C9	−112.4 (3)	C9—C10—C15—C14	−177.2 (3)
O3—N1—C8—C9	67.4 (4)	C13—C14—C15—C10	−0.1 (5)
O2—N1—C8—C7	116.9 (3)