Ethyl 2-amino-4-(2,4-di­chloro­phenyl)-4H-benzo­[f]­chromene-3-carboxyl­ate

The title compound, C₂₂H₁₇Cl₂NO₃, was synthesized by the reaction of 2-naphthol with 2,4-di­chloro­benz­aldehyde and ethyl cyano­acetate in ethanol in the presence of KF/Al₂O₃ as catalyst. X-ray analysis reveals that the pyran ring adopts a boat conformation. In the crystal structure, the amino group is involved in both intra- and intermolecular N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.127
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.38 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.38 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16      =       5.77 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Ethyl 2-amino-4-(2,4-dichlorophenyl)-4H-benzo[f]chromene-3-carboxylate

Crystal data

C22H17Cl2NO3	F(000) = 856
Mr = 414.27	Dx = 1.435 Mg m^−3
Monoclinic, P21/n	Melting point = 468–470 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.505 (2) Å	Cell parameters from 27 reflections
b = 9.037 (1) Å	θ = 2.9–15.2°
c = 14.913 (2) Å	µ = 0.36 mm^−1
β = 101.21 (1)°	T = 292 K
V = 1917.5 (4) Å^3	Block, colorless
Z = 4	0.56 × 0.52 × 0.24 mm

Data collection

Siemens P4 diffractometer	2292 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω scans	h = −10→17
Absorption correction: ψ scan (XSCANS; Siemens, 1994)	k = −5→10
Tmin = 0.770, Tmax = 0.917	l = −17→17
4195 measured reflections	3 standard reflections every 97 reflections
3379 independent reflections	intensity decay: 2.7%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0657P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3379 reflections	Δρmax = 0.43 e Å^−3
263 parameters	Δρmin = −0.26 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (13)

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.27601 (4)	0.20229 (9)	0.73019 (5)	0.0648 (3)
Cl2	0.33548 (6)	−0.14702 (11)	1.02538 (6)	0.0876 (3)
O1	0.64487 (11)	−0.0676 (2)	0.68554 (12)	0.0528 (5)
O2	0.48020 (13)	0.3596 (2)	0.73399 (17)	0.0740 (7)
O3	0.63744 (12)	0.3694 (2)	0.77851 (13)	0.0587 (5)
N	0.73094 (15)	0.1149 (3)	0.75533 (17)	0.0539 (6)
C1	0.64353 (16)	0.0722 (3)	0.71910 (16)	0.0421 (6)
C2	0.56205 (15)	0.1485 (3)	0.71608 (16)	0.0413 (6)
C3	0.46768 (15)	0.0718 (3)	0.68748 (16)	0.0400 (6)
H3	0.4230	0.1422	0.6530	0.048*
C4	0.47798 (16)	−0.0580 (3)	0.62602 (16)	0.0413 (6)
C5	0.56438 (17)	−0.1187 (3)	0.62734 (17)	0.0467 (6)
C6	0.5804 (2)	−0.2364 (3)	0.57188 (19)	0.0581 (8)
H6	0.6409	−0.2722	0.5744	0.070*
C7	0.5066 (2)	−0.2978 (3)	0.5144 (2)	0.0616 (8)
H7	0.5171	−0.3755	0.4767	0.074*
C8	0.4145 (2)	−0.2461 (3)	0.51043 (17)	0.0547 (7)
C9	0.3371 (3)	−0.3114 (4)	0.4523 (2)	0.0712 (9)
H9	0.3467	−0.3936	0.4177	0.085*
C10	0.2493 (3)	−0.2571 (5)	0.4458 (2)	0.0836 (11)
H10	0.1989	−0.3025	0.4077	0.100*
C11	0.2347 (2)	−0.1333 (4)	0.4961 (2)	0.0792 (10)
H11	0.1744	−0.0944	0.4896	0.095*
C12	0.30750 (19)	−0.0667 (4)	0.55543 (19)	0.0621 (8)
H12	0.2958	0.0150	0.5894	0.075*
C13	0.39960 (18)	−0.1224 (3)	0.56469 (17)	0.0482 (7)
C14	0.56613 (18)	0.2983 (3)	0.74640 (18)	0.0478 (6)
C15	0.4700 (2)	0.5032 (4)	0.7747 (3)	0.0897 (12)
H15A	0.4170	0.5558	0.7392	0.108*
H15B	0.5262	0.5620	0.7760	0.108*
C16	0.4551 (4)	0.4784 (5)	0.8672 (4)	0.1349 (19)
H16A	0.4047	0.4090	0.8659	0.162*
H16B	0.4392	0.5703	0.8927	0.162*
H16C	0.5115	0.4395	0.9042	0.162*
C17	0.43043 (15)	0.0218 (3)	0.77191 (16)	0.0398 (6)
C18	0.34755 (16)	0.0723 (3)	0.79615 (17)	0.0454 (6)
C19	0.31869 (18)	0.0218 (3)	0.87436 (18)	0.0541 (7)
H19	0.2631	0.0564	0.8891	0.065*
C20	0.37229 (19)	−0.0785 (3)	0.92902 (18)	0.0531 (7)
C21	0.45559 (19)	−0.1282 (3)	0.90977 (18)	0.0544 (7)
H21	0.4931	−0.1939	0.9489	0.065*
C22	0.48283 (17)	−0.0789 (3)	0.83091 (18)	0.0474 (6)
H22	0.5385	−0.1148	0.8170	0.057*
H1A	0.7381 (19)	0.2053 (15)	0.7733 (18)	0.059 (10)*
H1B	0.7763 (13)	0.063 (3)	0.7440 (18)	0.057 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0436 (4)	0.0748 (6)	0.0774 (5)	0.0162 (4)	0.0151 (3)	0.0091 (4)
Cl2	0.0930 (6)	0.1155 (8)	0.0611 (5)	−0.0267 (5)	0.0315 (4)	0.0129 (5)
O1	0.0423 (10)	0.0539 (12)	0.0607 (11)	0.0080 (9)	0.0064 (8)	−0.0081 (10)
O2	0.0478 (11)	0.0552 (13)	0.1188 (18)	0.0033 (10)	0.0160 (11)	−0.0241 (12)
O3	0.0487 (11)	0.0544 (12)	0.0753 (13)	−0.0145 (10)	0.0175 (9)	−0.0106 (10)
N	0.0346 (14)	0.0635 (18)	0.0631 (16)	0.0024 (13)	0.0083 (11)	−0.0037 (14)
C1	0.0364 (14)	0.0501 (16)	0.0406 (14)	−0.0025 (12)	0.0092 (11)	0.0031 (12)
C2	0.0321 (12)	0.0485 (15)	0.0443 (14)	−0.0027 (11)	0.0100 (10)	0.0001 (12)
C3	0.0344 (12)	0.0433 (14)	0.0425 (14)	0.0019 (11)	0.0080 (10)	0.0027 (12)
C4	0.0427 (14)	0.0424 (14)	0.0398 (13)	−0.0008 (12)	0.0104 (11)	0.0012 (12)
C5	0.0470 (15)	0.0484 (16)	0.0447 (14)	−0.0009 (13)	0.0087 (12)	−0.0023 (12)
C6	0.0645 (18)	0.0519 (17)	0.0591 (18)	0.0082 (15)	0.0152 (15)	−0.0049 (15)
C7	0.085 (2)	0.0514 (17)	0.0513 (17)	−0.0019 (17)	0.0220 (16)	−0.0084 (15)
C8	0.0712 (19)	0.0550 (17)	0.0380 (15)	−0.0156 (15)	0.0107 (14)	0.0008 (13)
C9	0.089 (2)	0.077 (2)	0.0470 (17)	−0.034 (2)	0.0123 (16)	−0.0087 (17)
C10	0.079 (2)	0.113 (3)	0.055 (2)	−0.046 (2)	0.0025 (18)	−0.010 (2)
C11	0.0513 (18)	0.121 (3)	0.062 (2)	−0.0208 (19)	0.0031 (15)	−0.003 (2)
C12	0.0484 (16)	0.084 (2)	0.0529 (17)	−0.0104 (16)	0.0066 (13)	−0.0060 (16)
C13	0.0505 (16)	0.0574 (17)	0.0376 (14)	−0.0125 (13)	0.0109 (12)	0.0035 (13)
C14	0.0400 (15)	0.0489 (16)	0.0575 (16)	−0.0046 (13)	0.0169 (12)	−0.0024 (14)
C15	0.069 (2)	0.063 (2)	0.144 (4)	−0.0006 (18)	0.035 (2)	−0.040 (2)
C16	0.148 (4)	0.095 (3)	0.173 (5)	−0.001 (3)	0.057 (4)	−0.053 (4)
C17	0.0328 (12)	0.0445 (15)	0.0425 (14)	−0.0043 (11)	0.0079 (10)	−0.0045 (12)
C18	0.0368 (13)	0.0481 (15)	0.0518 (15)	−0.0044 (12)	0.0100 (11)	−0.0055 (13)
C19	0.0428 (14)	0.069 (2)	0.0543 (16)	−0.0087 (14)	0.0190 (13)	−0.0098 (15)
C20	0.0561 (17)	0.0597 (18)	0.0455 (15)	−0.0187 (15)	0.0150 (13)	−0.0005 (14)
C21	0.0573 (17)	0.0521 (17)	0.0514 (16)	−0.0063 (14)	0.0047 (13)	0.0070 (14)
C22	0.0397 (14)	0.0491 (16)	0.0537 (16)	0.0023 (12)	0.0098 (12)	0.0035 (14)

Geometric parameters (Å, º)

Cl1—C18	1.740 (3)	C8—C13	1.421 (4)
Cl2—C20	1.741 (3)	C9—C10	1.351 (5)
O1—C1	1.361 (3)	C9—H9	0.9300
O1—C5	1.391 (3)	C10—C11	1.386 (5)
O2—C14	1.343 (3)	C10—H10	0.9300
O2—C15	1.452 (3)	C11—C12	1.378 (4)
O3—C14	1.233 (3)	C11—H11	0.9300
N—C1	1.335 (3)	C12—C13	1.409 (4)
N—H1A	0.859 (10)	C12—H12	0.9300
N—H1B	0.851 (10)	C15—C16	1.456 (6)
C1—C2	1.362 (3)	C15—H15A	0.9700
C2—C14	1.424 (3)	C15—H15B	0.9700
C2—C3	1.520 (3)	C16—H16A	0.9600
C3—C4	1.513 (3)	C16—H16B	0.9600
C3—C17	1.531 (3)	C16—H16C	0.9600
C3—H3	0.9800	C17—C22	1.386 (3)
C4—C5	1.365 (3)	C17—C18	1.397 (3)
C4—C13	1.436 (3)	C18—C19	1.391 (4)
C5—C6	1.394 (4)	C19—C20	1.358 (4)
C6—C7	1.353 (4)	C19—H19	0.9300
C6—H6	0.9300	C20—C21	1.371 (4)
C7—C8	1.406 (4)	C21—C22	1.385 (4)
C7—H7	0.9300	C21—H21	0.9300
C8—C9	1.407 (4)	C22—H22	0.9300
C1—O1—C5	117.88 (19)	C10—C11—H11	119.3
C14—O2—C15	118.6 (2)	C11—C12—C13	120.1 (3)
C1—N—H1A	116.7 (19)	C11—C12—H12	120.0
C1—N—H1B	118.1 (19)	C13—C12—H12	120.0
H1A—N—H1B	122 (3)	C12—C13—C8	118.1 (2)
N—C1—O1	109.7 (2)	C12—C13—C4	122.4 (3)
N—C1—C2	128.1 (3)	C8—C13—C4	119.5 (2)
O1—C1—C2	122.2 (2)	O3—C14—O2	121.6 (2)
C1—C2—C14	119.2 (2)	O3—C14—C2	126.8 (2)
C1—C2—C3	120.4 (2)	O2—C14—C2	111.6 (2)
C14—C2—C3	120.2 (2)	O2—C15—C16	107.7 (3)
C4—C3—C2	109.52 (19)	O2—C15—H15A	110.2
C4—C3—C17	111.2 (2)	C16—C15—H15A	110.2
C2—C3—C17	110.25 (19)	O2—C15—H15B	110.2
C4—C3—H3	108.6	C16—C15—H15B	110.2
C2—C3—H3	108.6	H15A—C15—H15B	108.5
C17—C3—H3	108.6	C15—C16—H16A	109.5
C5—C4—C13	117.2 (2)	C15—C16—H16B	109.5
C5—C4—C3	120.1 (2)	H16A—C16—H16B	109.5
C13—C4—C3	122.7 (2)	C15—C16—H16C	109.5
C4—C5—O1	122.2 (2)	H16A—C16—H16C	109.5
C4—C5—C6	123.8 (2)	H16B—C16—H16C	109.5
O1—C5—C6	114.0 (2)	C22—C17—C18	116.3 (2)
C7—C6—C5	119.1 (3)	C22—C17—C3	118.6 (2)
C7—C6—H6	120.4	C18—C17—C3	125.1 (2)
C5—C6—H6	120.4	C19—C18—C17	121.6 (2)
C6—C7—C8	121.2 (3)	C19—C18—Cl1	116.9 (2)
C6—C7—H7	119.4	C17—C18—Cl1	121.50 (19)
C8—C7—H7	119.4	C20—C19—C18	119.5 (2)
C7—C8—C9	121.6 (3)	C20—C19—H19	120.3
C7—C8—C13	119.1 (2)	C18—C19—H19	120.3
C9—C8—C13	119.3 (3)	C19—C20—C21	121.2 (2)
C10—C9—C8	121.3 (3)	C19—C20—Cl2	120.1 (2)
C10—C9—H9	119.3	C21—C20—Cl2	118.7 (2)
C8—C9—H9	119.3	C20—C21—C22	118.7 (3)
C9—C10—C11	119.7 (3)	C20—C21—H21	120.6
C9—C10—H10	120.2	C22—C21—H21	120.6
C11—C10—H10	120.2	C21—C22—C17	122.6 (2)
C12—C11—C10	121.4 (3)	C21—C22—H22	118.7
C12—C11—H11	119.3	C17—C22—H22	118.7
C5—O1—C1—N	−165.7 (2)	C7—C8—C13—C12	176.1 (3)
C5—O1—C1—C2	16.0 (3)	C9—C8—C13—C12	−2.2 (4)
N—C1—C2—C14	6.6 (4)	C7—C8—C13—C4	−3.5 (4)
O1—C1—C2—C14	−175.5 (2)	C9—C8—C13—C4	178.3 (2)
N—C1—C2—C3	−168.9 (2)	C5—C4—C13—C12	−178.2 (2)
O1—C1—C2—C3	9.1 (4)	C3—C4—C13—C12	1.8 (4)
C1—C2—C3—C4	−26.2 (3)	C5—C4—C13—C8	1.3 (4)
C14—C2—C3—C4	158.4 (2)	C3—C4—C13—C8	−178.7 (2)
C1—C2—C3—C17	96.4 (3)	C15—O2—C14—O3	−11.5 (4)
C14—C2—C3—C17	−79.0 (3)	C15—O2—C14—C2	170.0 (3)
C2—C3—C4—C5	20.8 (3)	C1—C2—C14—O3	−2.0 (4)
C17—C3—C4—C5	−101.3 (3)	C3—C2—C14—O3	173.5 (2)
C2—C3—C4—C13	−159.2 (2)	C1—C2—C14—O2	176.5 (2)
C17—C3—C4—C13	78.7 (3)	C3—C2—C14—O2	−8.1 (3)
C13—C4—C5—O1	−178.5 (2)	C14—O2—C15—C16	−87.6 (4)
C3—C4—C5—O1	1.5 (4)	C4—C3—C17—C22	60.5 (3)
C13—C4—C5—C6	1.2 (4)	C2—C3—C17—C22	−61.2 (3)
C3—C4—C5—C6	−178.8 (2)	C4—C3—C17—C18	−121.0 (3)
C1—O1—C5—C4	−21.6 (3)	C2—C3—C17—C18	117.3 (3)
C1—O1—C5—C6	158.7 (2)	C22—C17—C18—C19	−1.1 (4)
C4—C5—C6—C7	−1.6 (4)	C3—C17—C18—C19	−179.7 (2)
O1—C5—C6—C7	178.1 (2)	C22—C17—C18—Cl1	178.42 (19)
C5—C6—C7—C8	−0.7 (4)	C3—C17—C18—Cl1	−0.2 (3)
C6—C7—C8—C9	−178.6 (3)	C17—C18—C19—C20	0.3 (4)
C6—C7—C8—C13	3.2 (4)	Cl1—C18—C19—C20	−179.3 (2)
C7—C8—C9—C10	−177.0 (3)	C18—C19—C20—C21	1.6 (4)
C13—C8—C9—C10	1.3 (4)	C18—C19—C20—Cl2	−178.1 (2)
C8—C9—C10—C11	0.9 (5)	C19—C20—C21—C22	−2.6 (4)
C9—C10—C11—C12	−2.3 (5)	Cl2—C20—C21—C22	177.1 (2)
C10—C11—C12—C13	1.3 (5)	C20—C21—C22—C17	1.7 (4)
C11—C12—C13—C8	0.9 (4)	C18—C17—C22—C21	0.1 (4)
C11—C12—C13—C4	−179.5 (3)	C3—C17—C22—C21	178.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1A···O3	0.86 (1)	2.09 (2)	2.726 (3)	130 (2)
N—H1B···O3^i	0.85 (1)	2.22 (1)	3.033 (3)	161 (3)

Symmetry code: (i) −x+3/2, y−1/2, −z+3/2.