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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o478.
Published online 2010 January 30. doi:  10.1107/S1600536810002321
PMCID: PMC2979825

6,8-Di-tert-butyl-3-(4-nitro­phen­yl)-2H-chromen-2-one

Abstract

The title compound, C23H25NO4, was synthesized by the reaction of 2-(4-nitro­phen­yl)acetonitrile and 3,5-di-tert-butyl-2-hydroxy­benzaldehyde. The dihedral angle formed by the benzene ring and the mean plane through the benzopyran­one ring system is 35.57 (5)°. The nitro group is almost coplanar with the attached benzene ring [dihedral angle = 5.19 (15)°]. The crystal packing is stabilized by an inter­molecular C—H(...)O hydrogen-bond inter­action.

Related literature

For the applications and biological activity of coumarin deriv­atives, see: Tian et al. (2000 [triangle]); Fun et al. (2009 [triangle]).

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Object name is e-66-0o478-scheme1.jpg

Experimental

Crystal data

  • C23H25NO4
  • M r = 379.44
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o478-efi1.jpg
  • a = 14.6463 (13) Å
  • b = 11.8634 (10) Å
  • c = 23.604 (2) Å
  • V = 4101.3 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.20 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.982, T max = 1.000
  • 33748 measured reflections
  • 4736 independent reflections
  • 2809 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.140
  • S = 1.01
  • 4736 reflections
  • 254 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002321/rz2409sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002321/rz2409Isup2.hkl

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

Acknowledgments

This work was supported by Jiangsu Province Innovation Project No. CX07B-032z (XiaoFeng Zhou) and the Scientific Research Foundation of the Graduate School of Southeast University

supplementary crystallographic information

Comment

Coumarin (1-benzopyran-2-one) derivatives are a class of important organic compounds which have been found to be very useful in many applications as nonlinear optical materials, laser dyes, fluorescence materials, photorefractive materials, luminescence materials and as intermediates for drug synthesis (Tian et al., 2000). In addition, many natural coumarins possess a wide range of biological activities such as antifungal, antioxidant and antitumor activities (Fun et al. 2009). Herein the synthesis and crystal structure of the title compound is reported.

The molecular structure and atom-numbering scheme of the title compound are shown in Fig. 1. The C15—C16 bond is 1.347 (2) Å, which corresponds well to a typical C═C double bond. In addition, the C18—C16—C15 and C16—C15—C1 bond angles are almost equal (122.24 (15) and 122.66 (16)° respectively). The coumarin ring system, consisting of atoms C15, C16, C17, O1, O4 and C1—C6, is almost planar with a maximum deviation from the least-squares plane of 0.0442 (16) Å for atom O4. The phenyl ring attached at the C16 atom is twisted by a dihedral angle of 35.57 (5)°. The nitro group is slightly rotated about the C—N bond by 5.19 (15)°. The crystal packing is stabilized by an intermolecular C—H···O hydrogen bond (Table 1).

Experimental

2-(4-Nitrophenyl)acetonitrile (486 mg, 3 mmol) and 3,5-di-tert-butyl-2-hydroxybenzaldehyde (703 mg, 3 mmol) were dissolved in ethanol (20 ml) in a 50-ml round-bottom flask equipped with a magnetic stir bar and a water-cooled reflux condenser under nitrogen. The mixture was heated to reflux for 15 minutes, then three drops of piperidine and acetic acid were added. The solution was allowed to reflux for 4 h under nitrogen. After cooling, the reaction mixture was evaporated to dryness using a rotary evaporator to yield a yellow solid. The title compound was recrystallized from ethanol. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

All H atoms were located geometrically and treated as riding atoms, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity.

Crystal data

C23H25NO4F(000) = 1616
Mr = 379.44Dx = 1.229 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5698 reflections
a = 14.6463 (13) Åθ = 3.1–27.3°
b = 11.8634 (10) ŵ = 0.08 mm1
c = 23.604 (2) ÅT = 293 K
V = 4101.3 (6) Å3Block, yellow
Z = 80.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer4736 independent reflections
Radiation source: fine-focus sealed tube2809 reflections with I > 2σ(I)
graphiteRint = 0.053
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.2°
phi and ω scansh = −19→18
Absorption correction: multi-scan (SADABS; Bruker,2000)k = −15→15
Tmin = 0.982, Tmax = 1.000l = −30→26
33748 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.140w = 1/[σ2(Fo2) + (0.0615P)2 + 0.7021P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4736 reflectionsΔρmax = 0.19 e Å3
254 parametersΔρmin = −0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0021 (4)

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 (Å2)

xyzUiso*/Ueq
O10.14469 (8)0.87691 (10)0.19264 (5)0.0519 (3)
C10.04378 (11)0.96286 (14)0.12603 (7)0.0423 (4)
C20.05769 (11)0.88906 (14)0.17099 (7)0.0425 (4)
N10.50655 (12)1.22755 (18)0.01632 (8)0.0709 (5)
O20.49270 (12)1.31945 (18)−0.00487 (8)0.1067 (6)
C3−0.01328 (11)0.82746 (14)0.19572 (7)0.0434 (4)
O30.58048 (12)1.18104 (17)0.01503 (9)0.1104 (7)
C4−0.09936 (11)0.84849 (14)0.17326 (7)0.0459 (4)
H4A−0.14860.81070.18930.055*
C5−0.11757 (11)0.92252 (14)0.12817 (7)0.0433 (4)
C6−0.04451 (11)0.97845 (14)0.10493 (7)0.0452 (4)
H6A−0.05391.02740.07470.054*
C70.00116 (12)0.74480 (15)0.24487 (8)0.0503 (4)
C80.07354 (17)0.65680 (19)0.22987 (11)0.0861 (7)
H8A0.12990.69400.22080.129*
H8B0.05340.61370.19780.129*
H8C0.08280.60750.26160.129*
C90.02893 (15)0.8108 (2)0.29770 (8)0.0726 (6)
H9A0.08430.85160.29020.109*
H9B0.03860.75950.32860.109*
H9C−0.01870.86300.30750.109*
C10−0.08682 (14)0.68095 (18)0.25937 (9)0.0715 (6)
H10A−0.10620.63800.22710.107*
H10B−0.13370.73380.26950.107*
H10C−0.07570.63100.29060.107*
C11−0.21566 (11)0.94186 (15)0.10840 (7)0.0475 (4)
C12−0.26345 (13)0.82947 (18)0.09799 (10)0.0705 (6)
H12A−0.23160.78860.06900.106*
H12B−0.32520.84300.08610.106*
H12C−0.26370.78620.13230.106*
C13−0.26683 (13)1.00688 (19)0.15457 (9)0.0664 (6)
H13A−0.23711.07780.16110.100*
H13B−0.26690.96370.18900.100*
H13C−0.32861.01990.14260.100*
C14−0.21945 (13)1.0105 (2)0.05374 (9)0.0685 (6)
H14A−0.18951.08160.05950.103*
H14B−0.28201.02320.04340.103*
H14C−0.18920.96990.02400.103*
C150.12116 (11)1.02005 (14)0.10272 (7)0.0456 (4)
H15A0.11231.06840.07220.055*
C160.20632 (11)1.00669 (14)0.12319 (7)0.0447 (4)
C170.22005 (12)0.93221 (17)0.17162 (8)0.0529 (5)
C180.28618 (11)1.06494 (15)0.09819 (7)0.0461 (4)
C190.37009 (12)1.01170 (16)0.09219 (8)0.0565 (5)
H19A0.37760.93890.10600.068*
C200.44247 (12)1.06487 (18)0.06604 (8)0.0608 (5)
H20A0.49841.02860.06230.073*
C210.43052 (12)1.17234 (16)0.04563 (7)0.0538 (5)
C220.34929 (13)1.22816 (16)0.05115 (8)0.0578 (5)
H22A0.34251.30110.03730.069*
C230.27740 (12)1.17399 (16)0.07773 (8)0.0544 (5)
H23A0.22211.21150.08200.065*
O40.29087 (9)0.91451 (14)0.19558 (6)0.0807 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0473 (7)0.0605 (8)0.0480 (7)0.0011 (6)−0.0026 (5)0.0141 (6)
C10.0472 (9)0.0418 (9)0.0380 (9)0.0019 (7)0.0015 (7)0.0018 (7)
C20.0442 (9)0.0442 (9)0.0390 (9)0.0035 (7)−0.0014 (7)0.0002 (7)
N10.0655 (11)0.0793 (14)0.0680 (12)−0.0223 (10)0.0043 (9)0.0057 (10)
O20.0982 (13)0.1086 (15)0.1132 (15)−0.0251 (11)0.0095 (10)0.0500 (12)
C30.0530 (10)0.0385 (9)0.0387 (9)0.0006 (7)0.0008 (7)−0.0009 (7)
O30.0677 (10)0.1078 (14)0.1556 (18)−0.0113 (10)0.0351 (11)0.0174 (13)
C40.0496 (9)0.0436 (10)0.0445 (10)−0.0030 (7)0.0030 (7)0.0015 (8)
C50.0468 (9)0.0425 (9)0.0405 (9)0.0014 (7)−0.0001 (7)−0.0029 (8)
C60.0501 (10)0.0452 (10)0.0402 (9)0.0048 (8)−0.0018 (7)0.0055 (7)
C70.0563 (10)0.0488 (10)0.0458 (10)−0.0016 (8)−0.0010 (8)0.0084 (8)
C80.1032 (18)0.0653 (14)0.0898 (17)0.0275 (13)0.0165 (14)0.0257 (13)
C90.0846 (14)0.0847 (16)0.0485 (12)−0.0168 (12)−0.0113 (10)0.0076 (11)
C100.0800 (14)0.0669 (13)0.0676 (14)−0.0178 (11)−0.0094 (11)0.0259 (11)
C110.0448 (9)0.0492 (10)0.0486 (10)0.0028 (8)−0.0006 (7)0.0013 (8)
C120.0577 (12)0.0658 (14)0.0879 (16)−0.0063 (10)−0.0137 (10)−0.0057 (12)
C130.0577 (11)0.0726 (14)0.0691 (13)0.0102 (10)0.0083 (10)−0.0038 (11)
C140.0527 (10)0.0902 (16)0.0627 (13)0.0075 (10)−0.0050 (9)0.0145 (12)
C150.0504 (10)0.0468 (10)0.0396 (9)0.0006 (8)0.0013 (7)0.0060 (8)
C160.0455 (9)0.0467 (10)0.0420 (9)−0.0014 (7)0.0005 (7)0.0019 (8)
C170.0458 (9)0.0635 (12)0.0494 (10)−0.0002 (9)−0.0016 (8)0.0092 (9)
C180.0481 (9)0.0507 (10)0.0394 (9)−0.0027 (8)−0.0034 (7)−0.0001 (8)
C190.0533 (10)0.0557 (12)0.0604 (12)0.0012 (9)0.0013 (9)0.0089 (9)
C200.0484 (10)0.0694 (13)0.0646 (13)0.0002 (9)0.0032 (9)0.0039 (10)
C210.0540 (10)0.0600 (12)0.0473 (10)−0.0146 (9)0.0005 (8)−0.0002 (9)
C220.0650 (12)0.0484 (11)0.0600 (12)−0.0077 (9)−0.0025 (9)0.0054 (9)
C230.0519 (10)0.0514 (11)0.0600 (11)0.0008 (8)−0.0009 (8)0.0013 (9)
O40.0516 (8)0.1155 (13)0.0749 (10)−0.0047 (8)−0.0127 (7)0.0394 (9)

Geometric parameters (Å, °)

O1—C171.376 (2)C11—C121.526 (3)
O1—C21.3804 (19)C11—C141.527 (3)
C1—C21.391 (2)C11—C131.531 (2)
C1—C61.398 (2)C12—H12A0.9600
C1—C151.431 (2)C12—H12B0.9600
C2—C31.398 (2)C12—H12C0.9600
N1—O31.216 (2)C13—H13A0.9600
N1—O21.216 (2)C13—H13B0.9600
N1—C211.466 (2)C13—H13C0.9600
C3—C41.390 (2)C14—H14A0.9600
C3—C71.534 (2)C14—H14B0.9600
C4—C51.405 (2)C14—H14C0.9600
C4—H4A0.9300C15—C161.347 (2)
C5—C61.373 (2)C15—H15A0.9300
C5—C111.528 (2)C16—C171.459 (2)
C6—H6A0.9300C16—C181.481 (2)
C7—C91.528 (3)C17—O41.200 (2)
C7—C81.529 (3)C18—C231.387 (2)
C7—C101.533 (2)C18—C191.389 (2)
C8—H8A0.9600C19—C201.379 (2)
C8—H8B0.9600C19—H19A0.9300
C8—H8C0.9600C20—C211.374 (3)
C9—H9A0.9600C20—H20A0.9300
C9—H9B0.9600C21—C221.368 (3)
C9—H9C0.9600C22—C231.384 (2)
C10—H10A0.9600C22—H22A0.9300
C10—H10B0.9600C23—H23A0.9300
C10—H10C0.9600
C17—O1—C2123.84 (13)C12—C11—C5110.45 (15)
C2—C1—C6119.39 (15)C14—C11—C5111.87 (14)
C2—C1—C15118.41 (15)C13—C11—C5108.56 (14)
C6—C1—C15122.20 (15)C11—C12—H12A109.5
O1—C2—C1118.92 (14)C11—C12—H12B109.5
O1—C2—C3118.49 (14)H12A—C12—H12B109.5
C1—C2—C3122.59 (15)C11—C12—H12C109.5
O3—N1—O2123.03 (19)H12A—C12—H12C109.5
O3—N1—C21119.1 (2)H12B—C12—H12C109.5
O2—N1—C21117.90 (19)C11—C13—H13A109.5
C4—C3—C2114.90 (15)C11—C13—H13B109.5
C4—C3—C7121.89 (15)H13A—C13—H13B109.5
C2—C3—C7123.20 (14)C11—C13—H13C109.5
C3—C4—C5124.96 (15)H13A—C13—H13C109.5
C3—C4—H4A117.5H13B—C13—H13C109.5
C5—C4—H4A117.5C11—C14—H14A109.5
C6—C5—C4117.16 (15)C11—C14—H14B109.5
C6—C5—C11122.55 (15)H14A—C14—H14B109.5
C4—C5—C11120.24 (14)C11—C14—H14C109.5
C5—C6—C1120.96 (15)H14A—C14—H14C109.5
C5—C6—H6A119.5H14B—C14—H14C109.5
C1—C6—H6A119.5C16—C15—C1122.66 (16)
C9—C7—C3109.04 (15)C16—C15—H15A118.7
C9—C7—C8110.76 (17)C1—C15—H15A118.7
C3—C7—C8110.91 (15)C15—C16—C17118.68 (15)
C9—C7—C10107.15 (16)C15—C16—C18122.24 (15)
C3—C7—C10111.65 (14)C17—C16—C18119.07 (14)
C8—C7—C10107.27 (16)O4—C17—O1116.10 (16)
C7—C8—H8A109.5O4—C17—C16126.47 (17)
C7—C8—H8B109.5O1—C17—C16117.43 (14)
H8A—C8—H8B109.5C23—C18—C19118.07 (16)
C7—C8—H8C109.5C23—C18—C16120.05 (15)
H8A—C8—H8C109.5C19—C18—C16121.82 (16)
H8B—C8—H8C109.5C18—C19—C20121.18 (18)
C7—C9—H9A109.5C18—C19—H19A119.4
C7—C9—H9B109.5C20—C19—H19A119.4
H9A—C9—H9B109.5C21—C20—C19118.90 (18)
C7—C9—H9C109.5C21—C20—H20A120.5
H9A—C9—H9C109.5C19—C20—H20A120.5
H9B—C9—H9C109.5C22—C21—C20121.77 (17)
C7—C10—H10A109.5C22—C21—N1119.31 (18)
C7—C10—H10B109.5C20—C21—N1118.91 (18)
H10A—C10—H10B109.5C21—C22—C23118.69 (18)
C7—C10—H10C109.5C21—C22—H22A120.7
H10A—C10—H10C109.5C23—C22—H22A120.7
H10B—C10—H10C109.5C18—C23—C22121.37 (17)
C12—C11—C14108.27 (16)C18—C23—H23A119.3
C12—C11—C13109.29 (16)C22—C23—H23A119.3
C14—C11—C13108.35 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O2i0.932.553.409 (3)154

Symmetry codes: (i) x−1/2, −y+5/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2409).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fun, H.-K., Jebas, S. R., Parveen, M., Khanam, Z. & Ghalib, R. M. (2009). Acta Cryst. E65, o1322–o1323. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tian, Y., Akiyama, E., Nagase, Y., Kanazawa, A., Tsutsumi, O. & Ikeda, T. (2000). Macromol. Chem. Phys.201, 1640–1652.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography