Ethyl 2-amino-4-(3-chloro-phen-yl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxyl-ate.

The title mol-ecule, C(22)H(16)ClNO(5), was obtained by the reaction of (E)-ethyl 3-(3-chloro-phen-yl)-2-cyano-acrylate and 2-hydroxy-naphthalene-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 intra-molecular 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 ▶); Perchellet et al. (2001 ▶); Zhan et al. (2007 ▶). For natural products containing H-naphtho[2,3-b]pyran-5,10-dione, see: Jassbi et al. (2004 ▶); Rodriguez et al. (2003 ▶).

Experimental

Crystal data

C22H16ClNO5

M = 409.81

Triclinic,

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 ▶) 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 ▶); 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.

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

C22H16ClNO5	Z = 2
Mr = 409.81	F(000) = 424
Triclinic, P1	Dx = 1.512 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 6.1175 (17) Å	Cell parameters from 2873 reflections
b = 10.021 (3) Å	θ = 2.2–27.9°
c = 15.967 (5) Å	µ = 0.25 mm−1
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

Rigaku Saturn diffractometer	4261 independent reflections
Radiation source: rotating anode	3031 reflections with I > 2σ(I)
confocal	Rint = 0.033
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 2.2°
ω scans	h = −8→8
Absorption correction: multi-scan (Jacobson, 1998)	k = −13→13
Tmin = 0.924, Tmax = 0.952	l = −20→20
11338 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0583P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
4261 reflections	Δρmax = 0.37 e Å−3
272 parameters	Δρmin = −0.45 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (4)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.49377 (7)	0.57379 (4)	0.30597 (2)	0.02735 (12)
O1	−0.07224 (16)	0.26225 (11)	0.15817 (6)	0.0199 (2)
O2	0.68318 (17)	0.12419 (11)	−0.04552 (6)	0.0231 (2)
O3	0.75549 (16)	0.04439 (10)	0.11440 (5)	0.0172 (2)
O4	0.88099 (17)	−0.17355 (11)	0.35482 (6)	0.0225 (2)
O5	0.48890 (16)	−0.07946 (10)	0.38009 (6)	0.0184 (2)
N1	1.0294 (2)	−0.10163 (13)	0.20348 (8)	0.0191 (3)
C1	0.0990 (2)	0.23745 (14)	0.11164 (8)	0.0156 (3)
C2	0.0730 (2)	0.29181 (14)	0.02047 (8)	0.0162 (3)
C3	−0.1499 (2)	0.37702 (15)	−0.01112 (8)	0.0194 (3)
H3	−0.2854	0.3985	0.0244	0.023*
C4	−0.1737 (3)	0.43104 (16)	−0.09541 (9)	0.0223 (3)
H4	−0.3264	0.4885	−0.1173	0.027*
C5	0.0222 (3)	0.40187 (16)	−0.14729 (9)	0.0228 (3)
H5	0.0044	0.4412	−0.2042	0.027*
C6	0.2449 (3)	0.31522 (15)	−0.11653 (8)	0.0203 (3)
H6	0.3795	0.2939	−0.1524	0.024*
C7	0.2707 (2)	0.25930 (14)	−0.03244 (8)	0.0167 (3)
C8	0.5078 (2)	0.16626 (14)	−0.00028 (8)	0.0164 (3)
C9	0.5273 (2)	0.12298 (14)	0.09172 (8)	0.0155 (3)
C10	0.3409 (2)	0.15414 (14)	0.14472 (8)	0.0147 (3)
C11	0.3707 (2)	0.10501 (14)	0.23718 (8)	0.0148 (3)
H11	0.2601	0.0547	0.2528	0.018*
C12	0.6221 (2)	−0.00336 (14)	0.25298 (8)	0.0155 (3)
C13	0.7982 (2)	−0.02151 (14)	0.19472 (8)	0.0157 (3)
C14	0.3041 (2)	0.23611 (14)	0.28925 (8)	0.0145 (3)
C15	0.4265 (2)	0.32887 (14)	0.27878 (8)	0.0155 (3)
H15	0.5580	0.3086	0.2414	0.019*
C16	0.3534 (2)	0.45117 (15)	0.32365 (8)	0.0191 (3)
C17	0.1670 (3)	0.48205 (16)	0.38070 (8)	0.0233 (3)
H17	0.1203	0.5659	0.4111	0.028*
C18	0.0507 (3)	0.38732 (16)	0.39210 (9)	0.0238 (3)
H18	−0.0756	0.4055	0.4316	0.029*
C19	0.1165 (2)	0.26597 (16)	0.34642 (8)	0.0203 (3)
H19	0.0329	0.2030	0.3542	0.024*
C20	0.6813 (2)	−0.09205 (14)	0.33211 (8)	0.0163 (3)
C21	0.5361 (2)	−0.17302 (15)	0.45788 (8)	0.0199 (3)
H21A	0.6348	−0.1461	0.4955	0.024*
H21B	0.6222	−0.2754	0.4458	0.024*
C22	0.3031 (3)	−0.15439 (17)	0.49923 (9)	0.0251 (3)
H22A	0.3301	−0.2167	0.5518	0.030*
H22B	0.2069	−0.1814	0.4616	0.030*
H22C	0.2199	−0.0529	0.5113	0.030*
H1	1.081 (3)	−0.160 (2)	0.2506 (12)	0.037 (5)*
H2	1.111 (3)	−0.118 (2)	0.1561 (12)	0.044 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0303 (2)	0.01992 (19)	0.0328 (2)	−0.00981 (15)	−0.00537 (15)	−0.00406 (15)
O1	0.0141 (5)	0.0219 (5)	0.0218 (5)	−0.0057 (4)	0.0003 (4)	0.0018 (4)
O2	0.0216 (5)	0.0269 (6)	0.0188 (5)	−0.0069 (4)	0.0051 (4)	−0.0046 (4)
O3	0.0142 (5)	0.0194 (5)	0.0159 (5)	−0.0043 (4)	0.0011 (4)	−0.0011 (4)
O4	0.0178 (5)	0.0202 (5)	0.0229 (5)	−0.0005 (4)	−0.0025 (4)	0.0027 (4)
O5	0.0171 (5)	0.0179 (5)	0.0163 (5)	−0.0037 (4)	−0.0009 (4)	0.0048 (4)
N1	0.0145 (6)	0.0204 (6)	0.0194 (6)	−0.0033 (5)	0.0018 (5)	−0.0030 (5)
C1	0.0169 (7)	0.0139 (6)	0.0175 (6)	−0.0076 (5)	−0.0007 (5)	−0.0012 (5)
C2	0.0184 (7)	0.0141 (6)	0.0174 (7)	−0.0075 (5)	−0.0018 (5)	−0.0013 (5)
C3	0.0194 (7)	0.0183 (7)	0.0215 (7)	−0.0082 (6)	−0.0015 (5)	−0.0010 (6)
C4	0.0229 (7)	0.0205 (7)	0.0227 (7)	−0.0072 (6)	−0.0077 (6)	0.0006 (6)
C5	0.0305 (8)	0.0221 (7)	0.0168 (7)	−0.0110 (6)	−0.0037 (6)	0.0003 (6)
C6	0.0247 (8)	0.0211 (7)	0.0162 (7)	−0.0099 (6)	0.0006 (5)	−0.0020 (6)
C7	0.0207 (7)	0.0147 (6)	0.0168 (6)	−0.0086 (5)	−0.0009 (5)	−0.0029 (5)
C8	0.0197 (7)	0.0151 (6)	0.0171 (6)	−0.0090 (5)	0.0018 (5)	−0.0043 (5)
C9	0.0161 (7)	0.0137 (6)	0.0170 (6)	−0.0058 (5)	−0.0007 (5)	−0.0025 (5)
C10	0.0166 (7)	0.0125 (6)	0.0156 (6)	−0.0062 (5)	−0.0001 (5)	−0.0012 (5)
C11	0.0147 (6)	0.0144 (6)	0.0148 (6)	−0.0056 (5)	−0.0005 (5)	0.0015 (5)
C12	0.0145 (6)	0.0135 (6)	0.0172 (6)	−0.0036 (5)	−0.0005 (5)	−0.0015 (5)
C13	0.0169 (7)	0.0128 (6)	0.0175 (6)	−0.0056 (5)	−0.0024 (5)	−0.0021 (5)
C14	0.0132 (6)	0.0136 (6)	0.0121 (6)	−0.0004 (5)	−0.0020 (5)	0.0016 (5)
C15	0.0140 (6)	0.0165 (7)	0.0123 (6)	−0.0019 (5)	−0.0005 (5)	0.0003 (5)
C16	0.0217 (7)	0.0163 (7)	0.0163 (6)	−0.0040 (6)	−0.0060 (5)	0.0015 (5)
C17	0.0261 (8)	0.0181 (7)	0.0157 (7)	0.0032 (6)	−0.0041 (5)	−0.0027 (5)
C18	0.0205 (7)	0.0248 (8)	0.0155 (7)	0.0020 (6)	0.0035 (5)	0.0005 (6)
C19	0.0181 (7)	0.0217 (7)	0.0172 (7)	−0.0042 (6)	0.0005 (5)	0.0031 (5)
C20	0.0162 (7)	0.0125 (6)	0.0186 (7)	−0.0034 (5)	−0.0002 (5)	−0.0027 (5)
C21	0.0222 (7)	0.0181 (7)	0.0152 (6)	−0.0042 (6)	−0.0033 (5)	0.0047 (5)
C22	0.0244 (8)	0.0299 (8)	0.0195 (7)	−0.0102 (6)	−0.0016 (6)	0.0058 (6)

Cl1—C16	1.7479 (15)	C8—C9	1.4899 (18)
O1—C1	1.2177 (16)	C9—C10	1.3457 (18)
O2—C8	1.2231 (16)	C10—C11	1.5089 (17)
O3—C9	1.3584 (16)	C11—C12	1.5194 (18)
O3—C13	1.3751 (15)	C11—C14	1.5303 (19)
O4—C20	1.2274 (16)	C11—H11	1.0000
O5—C20	1.3492 (16)	C12—C13	1.3635 (18)
O5—C21	1.4549 (15)	C12—C20	1.4508 (18)
N1—C13	1.3372 (17)	C14—C19	1.3938 (18)
N1—H1	0.898 (18)	C14—C15	1.3959 (19)
N1—H2	0.880 (19)	C15—C16	1.3881 (19)
C1—C10	1.4834 (18)	C15—H15	0.9500
C1—C2	1.5002 (18)	C16—C17	1.387 (2)
C2—C3	1.3879 (19)	C17—C18	1.384 (2)
C2—C7	1.3959 (19)	C17—H17	0.9500
C3—C4	1.3963 (19)	C18—C19	1.390 (2)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.379 (2)	C19—H19	0.9500
C4—H4	0.9500	C21—C22	1.498 (2)
C5—C6	1.386 (2)	C21—H21A	0.9900
C5—H5	0.9500	C21—H21B	0.9900
C6—C7	1.3984 (18)	C22—H22A	0.9800
C6—H6	0.9500	C22—H22B	0.9800
C7—C8	1.4739 (19)	C22—H22C	0.9800
C9—O3—C13	118.10 (10)	C14—C11—H11	108.1
C20—O5—C21	115.05 (10)	C13—C12—C20	117.77 (11)
C13—N1—H1	119.2 (11)	C13—C12—C11	122.20 (11)
C13—N1—H2	115.0 (12)	C20—C12—C11	120.02 (11)
H1—N1—H2	121.7 (17)	N1—C13—C12	128.18 (12)
O1—C1—C10	120.28 (11)	N1—C13—O3	109.49 (11)
O1—C1—C2	121.46 (11)	C12—C13—O3	122.33 (11)
C10—C1—C2	118.25 (11)	C19—C14—C15	119.25 (12)
C3—C2—C7	119.80 (12)	C19—C14—C11	120.14 (12)
C3—C2—C1	119.51 (12)	C15—C14—C11	120.59 (11)
C7—C2—C1	120.68 (11)	C16—C15—C14	119.13 (12)
C2—C3—C4	119.58 (13)	C16—C15—H15	120.4
C2—C3—H3	120.2	C14—C15—H15	120.4
C4—C3—H3	120.2	C17—C16—C15	122.12 (14)
C5—C4—C3	120.69 (13)	C17—C16—Cl1	118.47 (11)
C5—C4—H4	119.7	C15—C16—Cl1	119.39 (11)
C3—C4—H4	119.7	C18—C17—C16	118.20 (13)
C4—C5—C6	120.06 (13)	C18—C17—H17	120.9
C4—C5—H5	120.0	C16—C17—H17	120.9
C6—C5—H5	120.0	C17—C18—C19	120.85 (13)
C5—C6—C7	119.77 (13)	C17—C18—H18	119.6
C5—C6—H6	120.1	C19—C18—H18	119.6
C7—C6—H6	120.1	C18—C19—C14	120.40 (14)
C2—C7—C6	120.06 (12)	C18—C19—H19	119.8
C2—C7—C8	120.43 (12)	C14—C19—H19	119.8
C6—C7—C8	119.50 (12)	O4—C20—O5	121.56 (12)
O2—C8—C7	122.97 (12)	O4—C20—C12	125.79 (12)
O2—C8—C9	120.19 (12)	O5—C20—C12	112.64 (11)
C7—C8—C9	116.84 (11)	O5—C21—C22	107.88 (11)
C10—C9—O3	124.60 (12)	O5—C21—H21A	110.1
C10—C9—C8	124.01 (12)	C22—C21—H21A	110.1
O3—C9—C8	111.36 (11)	O5—C21—H21B	110.1
C9—C10—C1	119.43 (11)	C22—C21—H21B	110.1
C9—C10—C11	121.75 (12)	H21A—C21—H21B	108.4
C1—C10—C11	118.82 (11)	C21—C22—H22A	109.5
C10—C11—C12	109.30 (10)	C21—C22—H22B	109.5
C10—C11—C14	110.13 (10)	H22A—C22—H22B	109.5
C12—C11—C14	112.83 (11)	C21—C22—H22C	109.5
C10—C11—H11	108.1	H22A—C22—H22C	109.5
C12—C11—H11	108.1	H22B—C22—H22C	109.5
O1—C1—C2—C3	2.5 (2)	C1—C10—C11—C12	168.17 (11)
C10—C1—C2—C3	−176.36 (12)	C9—C10—C11—C14	113.41 (14)
O1—C1—C2—C7	−178.39 (13)	C1—C10—C11—C14	−67.34 (15)
C10—C1—C2—C7	2.70 (19)	C10—C11—C12—C13	14.24 (18)
C7—C2—C3—C4	−0.8 (2)	C14—C11—C12—C13	−108.66 (14)
C1—C2—C3—C4	178.23 (12)	C10—C11—C12—C20	−165.61 (11)
C2—C3—C4—C5	−0.7 (2)	C14—C11—C12—C20	71.50 (15)
C3—C4—C5—C6	1.6 (2)	C20—C12—C13—N1	−7.3 (2)
C4—C5—C6—C7	−1.0 (2)	C11—C12—C13—N1	172.81 (13)
C3—C2—C7—C6	1.5 (2)	C20—C12—C13—O3	172.24 (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—N1	175.65 (11)
C1—C2—C7—C8	2.31 (19)	C9—O3—C13—C12	−4.00 (18)
C5—C6—C7—C2	−0.6 (2)	C10—C11—C14—C19	118.09 (13)
C5—C6—C7—C8	179.53 (13)	C12—C11—C14—C19	−119.49 (13)
C2—C7—C8—O2	173.40 (13)	C10—C11—C14—C15	−60.43 (15)
C6—C7—C8—O2	−6.7 (2)	C12—C11—C14—C15	62.00 (15)
C2—C7—C8—C9	−6.16 (18)	C19—C14—C15—C16	−2.01 (18)
C6—C7—C8—C9	173.74 (12)	C11—C14—C15—C16	176.52 (11)
C13—O3—C9—C10	7.43 (19)	C14—C15—C16—C17	2.07 (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—C10	5.37 (19)	Cl1—C16—C17—C18	177.61 (10)
O2—C8—C9—O3	3.80 (18)	C16—C17—C18—C19	−1.2 (2)
C7—C8—C9—O3	−176.63 (11)	C17—C18—C19—C14	1.2 (2)
O3—C9—C10—C1	−178.19 (12)	C15—C14—C19—C18	0.43 (19)
C8—C9—C10—C1	−0.5 (2)	C11—C14—C19—C18	−178.10 (12)
O3—C9—C10—C11	1.1 (2)	C21—O5—C20—O4	−2.29 (19)
C8—C9—C10—C11	178.79 (12)	C21—O5—C20—C12	176.26 (11)
O1—C1—C10—C9	177.45 (12)	C13—C12—C20—O4	6.9 (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—C11	177.09 (11)	C11—C12—C20—O5	8.26 (17)
C9—C10—C11—C12	−11.08 (17)	C20—O5—C21—C22	−175.25 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.898 (18)	2.049 (18)	2.6827 (17)	126.5 (15)
N1—H2···O2i	0.880 (19)	2.12 (2)	2.9913 (17)	170.2 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4	0.898 (18)	2.049 (18)	2.6827 (17)	126.5 (15)
N1—H2⋯O2i	0.880 (19)	2.12 (2)	2.9913 (17)	170.2 (18)

Symmetry code: (i) .