Ethyl 2-amino-4-(4-methoxy­phen­yl)-4H-benzo[h]chromene-3-carboxyl­ate

The title compound, C₂₃H₂₁NO₄, was synthesized by the reaction of 1-naphthol with ethyl cyano­caetate and 4-methoxy­benzaldehyde in ethanol under microwave irradiation. In the structure of C₂₃H₂₁NO₄, there are intra­molecular and intermolecular N–H...O hydrogen bonds, also C–H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.055
• wR factor = 0.184
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT480_ALERT_4_C Long H...A H-Bond Reported H22A   ..  CG2     ..       2.90 Ang.

   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

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

---

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Ethyl 2-amino-4-(4-methoxyphenyl)-4H-benzo[h]chromene-3-carboxylate

Crystal data

C23H21NO4	F(000) = 792
Mr = 375.41	Dx = 1.283 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.060 (2) Å	θ = 10–13°
b = 18.511 (4) Å	µ = 0.09 mm^−1
c = 8.9360 (18) Å	T = 293 K
β = 102.99 (3)°	Block, colourless
V = 1943.8 (7) Å^3	0.4 × 0.3 × 0.2 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.025
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.1°
Graphite monochromator	h = −14→14
ω/2θ scans	k = −22→0
4053 measured reflections	l = 0→11
3800 independent reflections	3 standard reflections every 200 reflections
2000 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.184	w = 1/[σ^2(Fo^2) + (0.09P)^2 + 0.2P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
3800 reflections	Δρmax = 0.18 e Å^−3
262 parameters	Δρmin = −0.22 e Å^−3
0 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: 0.0084 (19)

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
O1	0.6715 (2)	−0.22638 (11)	0.7492 (3)	0.0846 (7)
O2	0.69231 (15)	0.16586 (10)	0.5640 (2)	0.0550 (5)
O3	0.52120 (18)	0.16532 (11)	0.9261 (2)	0.0643 (6)
O4	0.63883 (17)	0.07651 (10)	1.0369 (2)	0.0629 (6)
N	0.5476 (2)	0.21060 (14)	0.6477 (3)	0.0596 (7)
C1	0.7365 (3)	−0.27841 (18)	0.8473 (6)	0.1104 (15)
H1A	0.7102	−0.3260	0.8138	0.166*
H1B	0.7281	−0.2709	0.9505	0.166*
H1C	0.8152	−0.2737	0.8440	0.166*
C2	0.6967 (2)	−0.15443 (15)	0.7802 (4)	0.0586 (8)
C3	0.6506 (2)	−0.10659 (15)	0.6632 (3)	0.0583 (7)
H3A	0.6049	−0.1237	0.5721	0.070*
C4	0.6724 (2)	−0.03385 (14)	0.6817 (3)	0.0517 (7)
H4A	0.6409	−0.0023	0.6026	0.062*
C5	0.7404 (2)	−0.00653 (14)	0.8161 (3)	0.0449 (6)
C6	0.7843 (2)	−0.05501 (16)	0.9315 (3)	0.0596 (8)
H6A	0.8296	−0.0380	1.0229	0.072*
C7	0.7626 (3)	−0.12805 (17)	0.9147 (4)	0.0638 (8)
H7A	0.7928	−0.1595	0.9946	0.077*
C8	0.7699 (2)	0.07347 (14)	0.8303 (3)	0.0481 (6)
H8A	0.8170	0.0817	0.9334	0.058*
C9	0.8411 (2)	0.09238 (14)	0.7147 (3)	0.0511 (7)
C10	0.9512 (2)	0.06370 (17)	0.7314 (4)	0.0697 (9)
H10A	0.9822	0.0363	0.8180	0.084*
C11	1.0134 (3)	0.07506 (19)	0.6241 (4)	0.0792 (10)
H11A	1.0864	0.0559	0.6390	0.095*
C12	0.9681 (3)	0.11582 (16)	0.4894 (4)	0.0648 (8)
C13	1.0271 (3)	0.12540 (19)	0.3697 (5)	0.0833 (11)
H13A	1.0997	0.1062	0.3801	0.100*
C14	0.9781 (3)	0.16244 (18)	0.2399 (5)	0.0876 (11)
H14A	1.0179	0.1680	0.1627	0.105*
C15	0.8698 (3)	0.19210 (18)	0.2205 (4)	0.0783 (10)
H15A	0.8374	0.2169	0.1308	0.094*
C16	0.8109 (3)	0.18462 (16)	0.3348 (4)	0.0652 (8)
H16A	0.7393	0.2055	0.3229	0.078*
C17	0.8580 (2)	0.14559 (13)	0.4700 (3)	0.0523 (7)
C18	0.7989 (2)	0.13317 (13)	0.5892 (3)	0.0485 (7)
C19	0.6359 (2)	0.16548 (13)	0.6811 (3)	0.0464 (6)
C20	0.6688 (2)	0.12318 (13)	0.8090 (3)	0.0482 (6)
C21	0.6020 (2)	0.12564 (14)	0.9249 (3)	0.0512 (7)
C22	0.5728 (3)	0.06875 (18)	1.1529 (3)	0.0697 (9)
H22A	0.4936	0.0593	1.1052	0.084*
H22B	0.5771	0.1125	1.2136	0.084*
C23	0.6229 (3)	0.0064 (2)	1.2524 (3)	0.0866 (11)
H23A	0.5815	−0.0006	1.3313	0.130*
H23B	0.7012	0.0164	1.2986	0.130*
H23C	0.6181	−0.0365	1.1909	0.130*
H2	0.498 (3)	0.2154 (15)	0.710 (4)	0.073 (9)*
H1	0.541 (3)	0.2434 (18)	0.576 (4)	0.084 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0973 (18)	0.0490 (13)	0.117 (2)	−0.0062 (11)	0.0449 (15)	0.0025 (13)
O2	0.0540 (11)	0.0619 (12)	0.0539 (11)	0.0099 (9)	0.0223 (9)	0.0086 (9)
O3	0.0774 (14)	0.0620 (12)	0.0608 (13)	0.0115 (11)	0.0313 (11)	−0.0014 (10)
O4	0.0778 (14)	0.0698 (12)	0.0470 (11)	0.0092 (10)	0.0263 (10)	0.0069 (10)
N	0.0606 (16)	0.0590 (16)	0.0659 (17)	0.0129 (12)	0.0288 (14)	0.0122 (14)
C1	0.109 (3)	0.051 (2)	0.182 (5)	0.0089 (19)	0.055 (3)	0.027 (2)
C2	0.0578 (17)	0.0494 (16)	0.077 (2)	0.0003 (13)	0.0335 (16)	0.0054 (15)
C3	0.0656 (18)	0.0565 (17)	0.0538 (17)	−0.0031 (14)	0.0154 (14)	−0.0083 (14)
C4	0.0621 (17)	0.0531 (16)	0.0401 (14)	0.0045 (13)	0.0117 (13)	0.0031 (12)
C5	0.0470 (14)	0.0509 (15)	0.0383 (13)	0.0042 (11)	0.0126 (11)	0.0032 (12)
C6	0.0616 (17)	0.0673 (19)	0.0481 (16)	0.0050 (14)	0.0083 (14)	0.0062 (14)
C7	0.0692 (19)	0.0622 (19)	0.062 (2)	0.0135 (15)	0.0200 (16)	0.0199 (16)
C8	0.0497 (15)	0.0530 (16)	0.0401 (14)	0.0000 (12)	0.0067 (12)	−0.0004 (12)
C9	0.0429 (15)	0.0546 (16)	0.0548 (16)	−0.0021 (12)	0.0092 (12)	−0.0020 (14)
C10	0.0512 (17)	0.080 (2)	0.075 (2)	0.0030 (15)	0.0086 (16)	0.0113 (18)
C11	0.0489 (17)	0.088 (2)	0.104 (3)	0.0077 (17)	0.0234 (18)	0.007 (2)
C12	0.0580 (18)	0.0593 (18)	0.084 (2)	−0.0024 (14)	0.0305 (17)	−0.0020 (17)
C13	0.068 (2)	0.079 (2)	0.116 (3)	0.0051 (18)	0.049 (2)	0.003 (2)
C14	0.100 (3)	0.072 (2)	0.113 (3)	0.002 (2)	0.071 (2)	0.006 (2)
C15	0.100 (3)	0.066 (2)	0.084 (2)	0.0085 (18)	0.052 (2)	0.0128 (17)
C16	0.073 (2)	0.0548 (17)	0.077 (2)	0.0059 (15)	0.0353 (17)	0.0094 (16)
C17	0.0555 (16)	0.0419 (14)	0.0649 (18)	−0.0040 (12)	0.0245 (14)	−0.0035 (13)
C18	0.0444 (14)	0.0460 (15)	0.0568 (17)	−0.0015 (12)	0.0151 (13)	−0.0034 (13)
C19	0.0498 (15)	0.0454 (14)	0.0477 (15)	−0.0034 (12)	0.0188 (12)	−0.0025 (12)
C20	0.0550 (16)	0.0448 (14)	0.0473 (15)	−0.0028 (12)	0.0168 (13)	−0.0032 (12)
C21	0.0636 (18)	0.0451 (15)	0.0459 (16)	−0.0014 (13)	0.0141 (14)	−0.0038 (13)
C22	0.085 (2)	0.085 (2)	0.0454 (16)	−0.0011 (18)	0.0292 (16)	0.0006 (16)
C23	0.106 (3)	0.104 (3)	0.0522 (19)	0.000 (2)	0.0237 (19)	0.0164 (19)

Geometric parameters (Å, º)

O1—C2	1.380 (3)	C8—H8A	0.9800
O1—C1	1.415 (4)	C9—C18	1.353 (4)
O2—C19	1.370 (3)	C9—C10	1.407 (4)
O2—C18	1.393 (3)	C10—C11	1.360 (4)
O3—C21	1.222 (3)	C10—H10A	0.9300
O4—C21	1.351 (3)	C11—C12	1.422 (4)
O4—C22	1.449 (3)	C11—H11A	0.9300
N—C19	1.333 (3)	C12—C17	1.412 (4)
N—H2	0.91 (3)	C12—C13	1.422 (4)
N—H1	0.87 (3)	C13—C14	1.362 (5)
C1—H1A	0.9600	C13—H13A	0.9300
C1—H1B	0.9600	C14—C15	1.391 (5)
C1—H1C	0.9600	C14—H14A	0.9300
C2—C7	1.373 (4)	C15—C16	1.376 (4)
C2—C3	1.387 (4)	C15—H15A	0.9300
C3—C4	1.375 (4)	C16—C17	1.413 (4)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C5	1.388 (3)	C17—C18	1.427 (4)
C4—H4A	0.9300	C19—C20	1.369 (4)
C5—C6	1.379 (3)	C20—C21	1.450 (4)
C5—C8	1.522 (4)	C22—C23	1.498 (4)
C6—C7	1.379 (4)	C22—H22A	0.9700
C6—H6A	0.9300	C22—H22B	0.9700
C7—H7A	0.9300	C23—H23A	0.9600
C8—C20	1.504 (4)	C23—H23B	0.9600
C8—C9	1.525 (4)	C23—H23C	0.9600
C2—O1—C1	117.8 (3)	C12—C11—H11A	119.6
C19—O2—C18	118.3 (2)	C17—C12—C11	118.8 (3)
C21—O4—C22	117.0 (2)	C17—C12—C13	118.3 (3)
C19—N—H2	121.7 (19)	C11—C12—C13	122.8 (3)
C19—N—H1	123 (2)	C14—C13—C12	120.6 (3)
H2—N—H1	115 (3)	C14—C13—H13A	119.7
O1—C1—H1A	109.5	C12—C13—H13A	119.7
O1—C1—H1B	109.5	C13—C14—C15	121.3 (3)
H1A—C1—H1B	109.5	C13—C14—H14A	119.4
O1—C1—H1C	109.5	C15—C14—H14A	119.4
H1A—C1—H1C	109.5	C16—C15—C14	119.7 (3)
H1B—C1—H1C	109.5	C16—C15—H15A	120.2
C7—C2—O1	125.2 (3)	C14—C15—H15A	120.2
C7—C2—C3	119.2 (3)	C15—C16—C17	120.7 (3)
O1—C2—C3	115.6 (3)	C15—C16—H16A	119.6
C4—C3—C2	120.1 (3)	C17—C16—H16A	119.6
C4—C3—H3A	120.0	C16—C17—C12	119.4 (3)
C2—C3—H3A	120.0	C16—C17—C18	123.3 (2)
C3—C4—C5	121.4 (3)	C12—C17—C18	117.3 (3)
C3—C4—H4A	119.3	C9—C18—O2	122.5 (2)
C5—C4—H4A	119.3	C9—C18—C17	123.5 (2)
C6—C5—C4	117.5 (3)	O2—C18—C17	114.0 (2)
C6—C5—C8	121.9 (2)	N—C19—C20	127.8 (2)
C4—C5—C8	120.5 (2)	N—C19—O2	109.6 (2)
C7—C6—C5	121.6 (3)	C20—C19—O2	122.6 (2)
C7—C6—H6A	119.2	C19—C20—C21	118.4 (2)
C5—C6—H6A	119.2	C19—C20—C8	122.0 (2)
C2—C7—C6	120.2 (3)	C21—C20—C8	119.6 (2)
C2—C7—H7A	119.9	O3—C21—O4	121.9 (3)
C6—C7—H7A	119.9	O3—C21—C20	126.7 (3)
C20—C8—C5	114.7 (2)	O4—C21—C20	111.4 (2)
C20—C8—C9	109.7 (2)	O4—C22—C23	106.7 (3)
C5—C8—C9	108.9 (2)	O4—C22—H22A	110.4
C20—C8—H8A	107.8	C23—C22—H22A	110.4
C5—C8—H8A	107.8	O4—C22—H22B	110.4
C9—C8—H8A	107.8	C23—C22—H22B	110.4
C18—C9—C10	117.9 (3)	H22A—C22—H22B	108.6
C18—C9—C8	121.7 (2)	C22—C23—H23A	109.5
C10—C9—C8	120.2 (3)	C22—C23—H23B	109.5
C11—C10—C9	121.6 (3)	H23A—C23—H23B	109.5
C11—C10—H10A	119.2	C22—C23—H23C	109.5
C9—C10—H10A	119.2	H23A—C23—H23C	109.5
C10—C11—C12	120.8 (3)	H23B—C23—H23C	109.5
C10—C11—H11A	119.6
C1—O1—C2—C7	−14.3 (4)	C11—C12—C17—C16	−178.4 (3)
C1—O1—C2—C3	165.5 (3)	C13—C12—C17—C16	−1.0 (4)
C7—C2—C3—C4	0.9 (4)	C11—C12—C17—C18	0.5 (4)
O1—C2—C3—C4	−178.8 (2)	C13—C12—C17—C18	177.9 (3)
C2—C3—C4—C5	0.1 (4)	C10—C9—C18—O2	−178.0 (2)
C3—C4—C5—C6	−0.8 (4)	C8—C9—C18—O2	5.9 (4)
C3—C4—C5—C8	175.9 (2)	C10—C9—C18—C17	3.1 (4)
C4—C5—C6—C7	0.5 (4)	C8—C9—C18—C17	−173.0 (2)
C8—C5—C6—C7	−176.2 (3)	C19—O2—C18—C9	9.9 (4)
O1—C2—C7—C6	178.5 (3)	C19—O2—C18—C17	−171.2 (2)
C3—C2—C7—C6	−1.2 (4)	C16—C17—C18—C9	176.1 (3)
C5—C6—C7—C2	0.5 (4)	C12—C17—C18—C9	−2.8 (4)
C6—C5—C8—C20	−124.4 (3)	C16—C17—C18—O2	−2.8 (4)
C4—C5—C8—C20	59.1 (3)	C12—C17—C18—O2	178.3 (2)
C6—C5—C8—C9	112.3 (3)	C18—O2—C19—N	167.9 (2)
C4—C5—C8—C9	−64.3 (3)	C18—O2—C19—C20	−12.8 (4)
C20—C8—C9—C18	−16.9 (3)	N—C19—C20—C21	0.4 (4)
C5—C8—C9—C18	109.4 (3)	O2—C19—C20—C21	−178.8 (2)
C20—C8—C9—C10	167.1 (2)	N—C19—C20—C8	178.9 (3)
C5—C8—C9—C10	−66.6 (3)	O2—C19—C20—C8	−0.2 (4)
C18—C9—C10—C11	−1.2 (5)	C5—C8—C20—C19	−108.7 (3)
C8—C9—C10—C11	174.9 (3)	C9—C8—C20—C19	14.2 (3)
C9—C10—C11—C12	−0.9 (5)	C5—C8—C20—C21	69.8 (3)
C10—C11—C12—C17	1.2 (5)	C9—C8—C20—C21	−167.3 (2)
C10—C11—C12—C13	−176.1 (3)	C22—O4—C21—O3	4.7 (4)
C17—C12—C13—C14	0.0 (5)	C22—O4—C21—C20	−174.6 (2)
C11—C12—C13—C14	177.3 (3)	C19—C20—C21—O3	−4.7 (4)
C12—C13—C14—C15	0.2 (6)	C8—C20—C21—O3	176.7 (3)
C13—C14—C15—C16	0.6 (6)	C19—C20—C21—O4	174.5 (2)
C14—C15—C16—C17	−1.6 (5)	C8—C20—C21—O4	−4.0 (3)
C15—C16—C17—C12	1.8 (4)	C21—O4—C22—C23	174.0 (2)
C15—C16—C17—C18	−177.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1···O3^i	0.87 (3)	2.14 (3)	3.002 (3)	172 (3)
N—H2···O3	0.91 (4)	2.10 (3)	2.711 (3)	123 (3)
N—H2···O1^ii	0.91 (4)	2.41 (4)	3.207 (4)	147 (3)
C4—H4A···Cg1	0.93	2.68	3.028 (1)	142
C22—H22A···Cg2^iii	0.97	2.90	3.636 (4)	134

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, −y, −z+2.