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Acta Cryst. (2009). E65, o1324    [ doi:10.1107/S160053680901753X ]

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

X. Hu, S. Lei and C.-S. Yao

Abstract top

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.

Comment top

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)

Related literature top

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

Experimental top

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 top

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).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2002); cell refinement: CrystalClear (Rigaku/MSC, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); 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
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The packing diagram of (I). Intermolecular hydrogen bonds are shown as dashed lines.
Ethyl 2-amino-4-(3-chlorophenyl)-5,10-dioxo-5,10-dihydro- 4H-benzo[g]chromene-3-carboxylate top
Crystal data top
C22H16ClNO5Z = 2
Mr = 409.81F000 = 424
Triclinic, P1Dx = 1.512 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71070 Å
a = 6.1175 (17) ÅCell parameters from 2873 reflections
b = 10.021 (3) Åθ = 2.2–27.9º
c = 15.967 (5) ŵ = 0.25 mm−1
α = 84.840 (13)ºT = 113 K
β = 87.714 (12)ºBlock, red
γ = 67.429 (8)º0.32 × 0.30 × 0.20 mm
V = 900.2 (4) Å3
Data collection top
Rigaku Saturn
diffractometer		4261 independent reflections
Radiation source: rotating anode3031 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.033
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113 Kθmin = 2.2º
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 top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034  w = 1/[σ2(Fo2) + (0.0583P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.097(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.37 e Å−3
4261 reflectionsΔρmin = −0.45 e Å−3
272 parametersExtinction 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)
Secondary atom site location: difference Fourier map
Crystal data top
C22H16ClNO5γ = 67.429 (8)º
Mr = 409.81V = 900.2 (4) Å3
Triclinic, P1Z = 2
a = 6.1175 (17) ÅMo Kα
b = 10.021 (3) ŵ = 0.25 mm−1
c = 15.967 (5) ÅT = 113 K
α = 84.840 (13)º0.32 × 0.30 × 0.20 mm
β = 87.714 (12)º
Data collection top
Rigaku Saturn
diffractometer		4261 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		3031 reflections with I > 2σ(I)
Tmin = 0.924, Tmax = 0.952Rint = 0.033
11338 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034272 parameters
wR(F2) = 0.097H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.37 e Å−3
4261 reflectionsΔρmin = −0.45 e Å−3
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
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
references
References top

Fujimoto, S. (2007). Biol. Pharm. Bull. 30, 1923–1929.

Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan.

Jassbi, A. R., Singh, P., Jain, S. & Tahara, S. (2004). Helv. Chim. Acta, 87, 820–824.

Perchellet, E. M., Sperfslage, B. J., Qabaja, G., Jones, G. B. & Perchellet, J.-P. (2001). Anti-Cancer Drugs, 12, 401–417.

Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA

Rodriguez, J. C., Fernandez Puentes, J. L., Baz, J. P. & Canedo, L. M. (2003). J. Antibiot. 56, 318–321.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhan, J. X., Burns, A. M., Liu, M. P. X., Faeth, S. H. & Gunatilaka, A. A. L. (2007). J. Nat. Prod. 70, 227–232.