3-Nitro-2-phenyl­chroman

Zhao, P.-H.; Hao, E.-J.; Liu, Y.-Q.; Zhao, G.-Z.

doi:10.1107/S1600536812020806

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1742

doi:10.1107/S1600536812020806

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3-Nitro-2-phenylchroman

Pei-Hua Zhao,^a ^* Er-Jun Hao,^b Ya-Qing Liu ^a and Gui-Zhe Zhao ^a

^aResearch Center for Engineering Technology of Polymeric Composites of Shanxi Province, College of Materials Science and Engineering, North University of China, Taiyuan 030051, People's Republic of China, and ^bKey Laboratory of Green Chemical Media and Reactions, Ministry of Education, College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: zph2004@yahoo.com.cn

(Received 8 May 2012; accepted 8 May 2012; online 16 May 2012)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.055
wR(F²) = 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020806/tk5093sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020806/tk5093Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020806/tk5093Isup3.cml

checkCIF report

Comment top

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)°.

Related literature top

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 top

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..

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 (Sheldrick, 2008).

Figures top

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.

3-Nitro-2-phenylchroman top

Crystal data top

C₁₅H₁₃NO₃	Z = 2
M_r = 255.26	F(000) = 268
Triclinic, P1	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0551P)²] where P = (F_o² + 2F_c²)/3
2205 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₅H₁₃NO₃	γ = 84.87 (3)°
M_r = 255.26	V = 626.6 (2) Å³
Triclinic, P1	Z = 2
a = 5.3769 (11) Å	Mo Kα radiation
b = 10.105 (2) Å	µ = 0.10 mm⁻¹
c = 12.320 (3) Å	T = 293 K
α = 70.85 (3)°	0.20 × 0.20 × 0.10 mm
β = 82.89 (3)°

Data collection top

Rigaku Saturn diffractometer	2205 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	912 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.991	R_int = 0.053
5249 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.07	Δρ_max = 0.47 e Å⁻³
2205 reflections	Δρ_min = −0.31 e Å⁻³
172 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃NO₃
M_r	255.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.3769 (11), 10.105 (2), 12.320 (3)
α, β, γ (°)	70.85 (3), 82.89 (3), 84.87 (3)
V (Å³)	626.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.981, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5249, 2205, 912
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.152, 1.07
No. of reflections	2205
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.31

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the Start-up Foundation of North University of China and the Youth Foundation of North University of China.

References

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