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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1324.
Published online 2009 May 20. doi:  10.1107/S160053680901753X
PMCID: PMC2969697

Ethyl 2-amino-4-(3-chloro­phen­yl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxyl­ate

Abstract

The title mol­ecule, C22H16ClNO5, was obtained by the reaction of (E)-ethyl 3-(3-chloro­phen­yl)-2-cyano­acrylate and 2-hydroxy­naphthalene-1,4-dione catalysed by triethylamine in ethanol. In the crystal structure, the chlorobenzene ring makes a dihedral angle of 88.63 (4)° with the fused ring system. The six-membered ring formed by an intra­molecular N—H(...)O hydrogen bond is almost planar. The crystal packing is stabilized by N—H(...)O hydrogen bonds.

Related literature

For the anti­tumor activity of 4H-naphtho[2,3-b]pyran-5,10-dione derivatives, see: Fujimoto (2007 [triangle]); Perchellet et al. (2001 [triangle]); Zhan et al. (2007 [triangle]). For natural products containing H-naphtho[2,3-b]pyran-5,10-dione, see: Jassbi et al. (2004 [triangle]); Rodriguez et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1324-scheme1.jpg

Experimental

Crystal data

  • C22H16ClNO5
  • M r = 409.81
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1324-efi1.jpg
  • a = 6.1175 (17) Å
  • b = 10.021 (3) Å
  • c = 15.967 (5) Å
  • α = 84.840 (13)°
  • β = 87.714 (12)°
  • γ = 67.429 (8)°
  • V = 900.2 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 113 K
  • 0.32 × 0.30 × 0.20 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (Jacobson, 1998 [triangle]) T min = 0.924, T max = 0.952
  • 11338 measured reflections
  • 4261 independent reflections
  • 3031 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.097
  • S = 1.01
  • 4261 reflections
  • 272 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.45 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2002 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901753X/hg2512sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901753X/hg2512Isup2.hkl

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

supplementary crystallographic information

Comment

The derivatives of 4H-naphtho[2,3-b]pyran-5,10-dione have antitumor activities (Fujimoto, 2007; Zhan et al., 2007; Perchellet et al., 2001). Besides, some natural products also contain this moiety (Rodriguez et al., 2003; Jassbi et al., 2004). In order to develop new potential antitumor chemicals, a series of novel 4H-naphtho[2,3-b]pyran-5,10-dione derivatives based on the scaffolds of natural products have been synthesized. However, to the best of our knowledge, there are no reports on the crystal structure of these compounds. Determination of the molecular structure is crucial to the study of the structure and activity relationship. Here we report the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. It consists of five rings, considering the six-membered ring formed by the intramolecular N1—H1···O4 hydrogen bond (Table 1). The dihedral angles between the neighbouring rings show that the naphthalene ring and the pyran ring in an envelope conformation are almost coplanar. The phenyl ring bonded to the pyrans ring is almost perpendicular to the fused ring, for the dihedral angle is 88.63 (4)°. In the molecular structure, the crystal packing is stabilized N1—H2···O2 intermolecular hydrogen bonds. (Figs.2, Table 1)

Experimental

The title compound was synthesized by the reaction of (E)-ethyl 3-(3-chlorophenyl)-2-cyanoacrylate (1 mmol) and 2-hydroxynaphthalene-1,4-dione (1 mmol) catalyzed by Et3N in 15 ml ethanol at reluxing temperature. After cooling, the solvent was removed at reduced pressure and the residue was washed with water and recrystallized from ethanol, which gave single crystals suitable for X-ray diffraction.

Refinement

The hydrogen atoms bonded to nitrogen atom was positioned from a Fourier difference map and were refined freely. Other H atoms were placed in calculated positions, with C—H = 0.95-1.00 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq (parent atom).

Figures

Fig. 1.
The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The packing diagram of (I). Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C22H16ClNO5Z = 2
Mr = 409.81F(000) = 424
Triclinic, P1Dx = 1.512 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 6.1175 (17) ÅCell parameters from 2873 reflections
b = 10.021 (3) Åθ = 2.2–27.9°
c = 15.967 (5) ŵ = 0.25 mm1
α = 84.840 (13)°T = 113 K
β = 87.714 (12)°Block, red
γ = 67.429 (8)°0.32 × 0.30 × 0.20 mm
V = 900.2 (4) Å3

Data collection

Rigaku Saturn diffractometer4261 independent reflections
Radiation source: rotating anode3031 reflections with I > 2σ(I)
confocalRint = 0.033
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.2°
ω scansh = −8→8
Absorption correction: multi-scan (Jacobson, 1998)k = −13→13
Tmin = 0.924, Tmax = 0.952l = −20→20
11338 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)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097w = 1/[σ2(Fo2) + (0.0583P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4261 reflectionsΔρmax = 0.37 e Å3
272 parametersΔρmin = −0.45 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: 0.020 (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
Cl10.49377 (7)0.57379 (4)0.30597 (2)0.02735 (12)
O1−0.07224 (16)0.26225 (11)0.15817 (6)0.0199 (2)
O20.68318 (17)0.12419 (11)−0.04552 (6)0.0231 (2)
O30.75549 (16)0.04439 (10)0.11440 (5)0.0172 (2)
O40.88099 (17)−0.17355 (11)0.35482 (6)0.0225 (2)
O50.48890 (16)−0.07946 (10)0.38009 (6)0.0184 (2)
N11.0294 (2)−0.10163 (13)0.20348 (8)0.0191 (3)
C10.0990 (2)0.23745 (14)0.11164 (8)0.0156 (3)
C20.0730 (2)0.29181 (14)0.02047 (8)0.0162 (3)
C3−0.1499 (2)0.37702 (15)−0.01112 (8)0.0194 (3)
H3−0.28540.39850.02440.023*
C4−0.1737 (3)0.43104 (16)−0.09541 (9)0.0223 (3)
H4−0.32640.4885−0.11730.027*
C50.0222 (3)0.40187 (16)−0.14729 (9)0.0228 (3)
H50.00440.4412−0.20420.027*
C60.2449 (3)0.31522 (15)−0.11653 (8)0.0203 (3)
H60.37950.2939−0.15240.024*
C70.2707 (2)0.25930 (14)−0.03244 (8)0.0167 (3)
C80.5078 (2)0.16626 (14)−0.00028 (8)0.0164 (3)
C90.5273 (2)0.12298 (14)0.09172 (8)0.0155 (3)
C100.3409 (2)0.15414 (14)0.14472 (8)0.0147 (3)
C110.3707 (2)0.10501 (14)0.23718 (8)0.0148 (3)
H110.26010.05470.25280.018*
C120.6221 (2)−0.00336 (14)0.25298 (8)0.0155 (3)
C130.7982 (2)−0.02151 (14)0.19472 (8)0.0157 (3)
C140.3041 (2)0.23611 (14)0.28925 (8)0.0145 (3)
C150.4265 (2)0.32887 (14)0.27878 (8)0.0155 (3)
H150.55800.30860.24140.019*
C160.3534 (2)0.45117 (15)0.32365 (8)0.0191 (3)
C170.1670 (3)0.48205 (16)0.38070 (8)0.0233 (3)
H170.12030.56590.41110.028*
C180.0507 (3)0.38732 (16)0.39210 (9)0.0238 (3)
H18−0.07560.40550.43160.029*
C190.1165 (2)0.26597 (16)0.34642 (8)0.0203 (3)
H190.03290.20300.35420.024*
C200.6813 (2)−0.09205 (14)0.33211 (8)0.0163 (3)
C210.5361 (2)−0.17302 (15)0.45788 (8)0.0199 (3)
H21A0.6348−0.14610.49550.024*
H21B0.6222−0.27540.44580.024*
C220.3031 (3)−0.15439 (17)0.49923 (9)0.0251 (3)
H22A0.3301−0.21670.55180.030*
H22B0.2069−0.18140.46160.030*
H22C0.2199−0.05290.51130.030*
H11.081 (3)−0.160 (2)0.2506 (12)0.037 (5)*
H21.111 (3)−0.118 (2)0.1561 (12)0.044 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0303 (2)0.01992 (19)0.0328 (2)−0.00981 (15)−0.00537 (15)−0.00406 (15)
O10.0141 (5)0.0219 (5)0.0218 (5)−0.0057 (4)0.0003 (4)0.0018 (4)
O20.0216 (5)0.0269 (6)0.0188 (5)−0.0069 (4)0.0051 (4)−0.0046 (4)
O30.0142 (5)0.0194 (5)0.0159 (5)−0.0043 (4)0.0011 (4)−0.0011 (4)
O40.0178 (5)0.0202 (5)0.0229 (5)−0.0005 (4)−0.0025 (4)0.0027 (4)
O50.0171 (5)0.0179 (5)0.0163 (5)−0.0037 (4)−0.0009 (4)0.0048 (4)
N10.0145 (6)0.0204 (6)0.0194 (6)−0.0033 (5)0.0018 (5)−0.0030 (5)
C10.0169 (7)0.0139 (6)0.0175 (6)−0.0076 (5)−0.0007 (5)−0.0012 (5)
C20.0184 (7)0.0141 (6)0.0174 (7)−0.0075 (5)−0.0018 (5)−0.0013 (5)
C30.0194 (7)0.0183 (7)0.0215 (7)−0.0082 (6)−0.0015 (5)−0.0010 (6)
C40.0229 (7)0.0205 (7)0.0227 (7)−0.0072 (6)−0.0077 (6)0.0006 (6)
C50.0305 (8)0.0221 (7)0.0168 (7)−0.0110 (6)−0.0037 (6)0.0003 (6)
C60.0247 (8)0.0211 (7)0.0162 (7)−0.0099 (6)0.0006 (5)−0.0020 (6)
C70.0207 (7)0.0147 (6)0.0168 (6)−0.0086 (5)−0.0009 (5)−0.0029 (5)
C80.0197 (7)0.0151 (6)0.0171 (6)−0.0090 (5)0.0018 (5)−0.0043 (5)
C90.0161 (7)0.0137 (6)0.0170 (6)−0.0058 (5)−0.0007 (5)−0.0025 (5)
C100.0166 (7)0.0125 (6)0.0156 (6)−0.0062 (5)−0.0001 (5)−0.0012 (5)
C110.0147 (6)0.0144 (6)0.0148 (6)−0.0056 (5)−0.0005 (5)0.0015 (5)
C120.0145 (6)0.0135 (6)0.0172 (6)−0.0036 (5)−0.0005 (5)−0.0015 (5)
C130.0169 (7)0.0128 (6)0.0175 (6)−0.0056 (5)−0.0024 (5)−0.0021 (5)
C140.0132 (6)0.0136 (6)0.0121 (6)−0.0004 (5)−0.0020 (5)0.0016 (5)
C150.0140 (6)0.0165 (7)0.0123 (6)−0.0019 (5)−0.0005 (5)0.0003 (5)
C160.0217 (7)0.0163 (7)0.0163 (6)−0.0040 (6)−0.0060 (5)0.0015 (5)
C170.0261 (8)0.0181 (7)0.0157 (7)0.0032 (6)−0.0041 (5)−0.0027 (5)
C180.0205 (7)0.0248 (8)0.0155 (7)0.0020 (6)0.0035 (5)0.0005 (6)
C190.0181 (7)0.0217 (7)0.0172 (7)−0.0042 (6)0.0005 (5)0.0031 (5)
C200.0162 (7)0.0125 (6)0.0186 (7)−0.0034 (5)−0.0002 (5)−0.0027 (5)
C210.0222 (7)0.0181 (7)0.0152 (6)−0.0042 (6)−0.0033 (5)0.0047 (5)
C220.0244 (8)0.0299 (8)0.0195 (7)−0.0102 (6)−0.0016 (6)0.0058 (6)

Geometric parameters (Å, °)

Cl1—C161.7479 (15)C8—C91.4899 (18)
O1—C11.2177 (16)C9—C101.3457 (18)
O2—C81.2231 (16)C10—C111.5089 (17)
O3—C91.3584 (16)C11—C121.5194 (18)
O3—C131.3751 (15)C11—C141.5303 (19)
O4—C201.2274 (16)C11—H111.0000
O5—C201.3492 (16)C12—C131.3635 (18)
O5—C211.4549 (15)C12—C201.4508 (18)
N1—C131.3372 (17)C14—C191.3938 (18)
N1—H10.898 (18)C14—C151.3959 (19)
N1—H20.880 (19)C15—C161.3881 (19)
C1—C101.4834 (18)C15—H150.9500
C1—C21.5002 (18)C16—C171.387 (2)
C2—C31.3879 (19)C17—C181.384 (2)
C2—C71.3959 (19)C17—H170.9500
C3—C41.3963 (19)C18—C191.390 (2)
C3—H30.9500C18—H180.9500
C4—C51.379 (2)C19—H190.9500
C4—H40.9500C21—C221.498 (2)
C5—C61.386 (2)C21—H21A0.9900
C5—H50.9500C21—H21B0.9900
C6—C71.3984 (18)C22—H22A0.9800
C6—H60.9500C22—H22B0.9800
C7—C81.4739 (19)C22—H22C0.9800
C9—O3—C13118.10 (10)C14—C11—H11108.1
C20—O5—C21115.05 (10)C13—C12—C20117.77 (11)
C13—N1—H1119.2 (11)C13—C12—C11122.20 (11)
C13—N1—H2115.0 (12)C20—C12—C11120.02 (11)
H1—N1—H2121.7 (17)N1—C13—C12128.18 (12)
O1—C1—C10120.28 (11)N1—C13—O3109.49 (11)
O1—C1—C2121.46 (11)C12—C13—O3122.33 (11)
C10—C1—C2118.25 (11)C19—C14—C15119.25 (12)
C3—C2—C7119.80 (12)C19—C14—C11120.14 (12)
C3—C2—C1119.51 (12)C15—C14—C11120.59 (11)
C7—C2—C1120.68 (11)C16—C15—C14119.13 (12)
C2—C3—C4119.58 (13)C16—C15—H15120.4
C2—C3—H3120.2C14—C15—H15120.4
C4—C3—H3120.2C17—C16—C15122.12 (14)
C5—C4—C3120.69 (13)C17—C16—Cl1118.47 (11)
C5—C4—H4119.7C15—C16—Cl1119.39 (11)
C3—C4—H4119.7C18—C17—C16118.20 (13)
C4—C5—C6120.06 (13)C18—C17—H17120.9
C4—C5—H5120.0C16—C17—H17120.9
C6—C5—H5120.0C17—C18—C19120.85 (13)
C5—C6—C7119.77 (13)C17—C18—H18119.6
C5—C6—H6120.1C19—C18—H18119.6
C7—C6—H6120.1C18—C19—C14120.40 (14)
C2—C7—C6120.06 (12)C18—C19—H19119.8
C2—C7—C8120.43 (12)C14—C19—H19119.8
C6—C7—C8119.50 (12)O4—C20—O5121.56 (12)
O2—C8—C7122.97 (12)O4—C20—C12125.79 (12)
O2—C8—C9120.19 (12)O5—C20—C12112.64 (11)
C7—C8—C9116.84 (11)O5—C21—C22107.88 (11)
C10—C9—O3124.60 (12)O5—C21—H21A110.1
C10—C9—C8124.01 (12)C22—C21—H21A110.1
O3—C9—C8111.36 (11)O5—C21—H21B110.1
C9—C10—C1119.43 (11)C22—C21—H21B110.1
C9—C10—C11121.75 (12)H21A—C21—H21B108.4
C1—C10—C11118.82 (11)C21—C22—H22A109.5
C10—C11—C12109.30 (10)C21—C22—H22B109.5
C10—C11—C14110.13 (10)H22A—C22—H22B109.5
C12—C11—C14112.83 (11)C21—C22—H22C109.5
C10—C11—H11108.1H22A—C22—H22C109.5
C12—C11—H11108.1H22B—C22—H22C109.5
O1—C1—C2—C32.5 (2)C1—C10—C11—C12168.17 (11)
C10—C1—C2—C3−176.36 (12)C9—C10—C11—C14113.41 (14)
O1—C1—C2—C7−178.39 (13)C1—C10—C11—C14−67.34 (15)
C10—C1—C2—C72.70 (19)C10—C11—C12—C1314.24 (18)
C7—C2—C3—C4−0.8 (2)C14—C11—C12—C13−108.66 (14)
C1—C2—C3—C4178.23 (12)C10—C11—C12—C20−165.61 (11)
C2—C3—C4—C5−0.7 (2)C14—C11—C12—C2071.50 (15)
C3—C4—C5—C61.6 (2)C20—C12—C13—N1−7.3 (2)
C4—C5—C6—C7−1.0 (2)C11—C12—C13—N1172.81 (13)
C3—C2—C7—C61.5 (2)C20—C12—C13—O3172.24 (11)
C1—C2—C7—C6−177.59 (12)C11—C12—C13—O3−7.6 (2)
C3—C2—C7—C8−178.63 (12)C9—O3—C13—N1175.65 (11)
C1—C2—C7—C82.31 (19)C9—O3—C13—C12−4.00 (18)
C5—C6—C7—C2−0.6 (2)C10—C11—C14—C19118.09 (13)
C5—C6—C7—C8179.53 (13)C12—C11—C14—C19−119.49 (13)
C2—C7—C8—O2173.40 (13)C10—C11—C14—C15−60.43 (15)
C6—C7—C8—O2−6.7 (2)C12—C11—C14—C1562.00 (15)
C2—C7—C8—C9−6.16 (18)C19—C14—C15—C16−2.01 (18)
C6—C7—C8—C9173.74 (12)C11—C14—C15—C16176.52 (11)
C13—O3—C9—C107.43 (19)C14—C15—C16—C172.07 (19)
C13—O3—C9—C8−170.55 (10)C14—C15—C16—Cl1−176.00 (9)
O2—C8—C9—C10−174.20 (13)C15—C16—C17—C18−0.47 (19)
C7—C8—C9—C105.37 (19)Cl1—C16—C17—C18177.61 (10)
O2—C8—C9—O33.80 (18)C16—C17—C18—C19−1.2 (2)
C7—C8—C9—O3−176.63 (11)C17—C18—C19—C141.2 (2)
O3—C9—C10—C1−178.19 (12)C15—C14—C19—C180.43 (19)
C8—C9—C10—C1−0.5 (2)C11—C14—C19—C18−178.10 (12)
O3—C9—C10—C111.1 (2)C21—O5—C20—O4−2.29 (19)
C8—C9—C10—C11178.79 (12)C21—O5—C20—C12176.26 (11)
O1—C1—C10—C9177.45 (12)C13—C12—C20—O46.9 (2)
C2—C1—C10—C9−3.64 (19)C11—C12—C20—O4−173.26 (13)
O1—C1—C10—C11−1.82 (19)C13—C12—C20—O5−171.59 (12)
C2—C1—C10—C11177.09 (11)C11—C12—C20—O58.26 (17)
C9—C10—C11—C12−11.08 (17)C20—O5—C21—C22−175.25 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O40.898 (18)2.049 (18)2.6827 (17)126.5 (15)
N1—H2···O2i0.880 (19)2.12 (2)2.9913 (17)170.2 (18)

Symmetry codes: (i) −x+2, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2512).

References

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