Methyl 3-amino-1-(3-nitro­phen­yl)-1H-naphtho[2,1-b]pyran-2-carboxyl­ate

The title compound, C₂₁H₁₆N₂O₅, was synthesized by the reaction of 2-naphthol with methyl cyano­acetate and 3-nitro­benzaldehyde in ethanol under microwave irradiation. The pyran ring adopts a boat conformation.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.062
• wR factor = 0.186
• Data-to-parameter ratio = 13.7

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
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.90 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.33 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 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
   3 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

---

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.

Methyl 3-amino-1-(3-nitrophenyl)-1H-naphtho[2,1-b]furan-2-carboxylate

Crystal data

C21H16N2O5	F(000) = 784
Mr = 376.36	Dx = 1.403 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.094 (2) Å	θ = 10–13°
b = 8.5620 (17) Å	µ = 0.10 mm^−1
c = 18.186 (4) Å	T = 293 K
β = 108.92 (3)°	Block, colourless
V = 1781.4 (7) Å^3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.021
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 1.8°
Graphite monochromator	h = 0→14
ω/2θ scans	k = 0→10
3659 measured reflections	l = −22→21
3490 independent reflections	3 standard reflections every 200 reflections
2032 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)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.09P)^2 + 0.27P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3490 reflections	Δρmax = 0.23 e Å^−3
254 parameters	Δρmin = −0.19 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: 0.017 (3)

Special details

Experimental. ¹H NMR (CDCl₃): δ 8.20 (d, 1H), 7.93 (d, 1H), 7.88 (d, 1H), 7.79 (t, 2H), 7.56–7.59 (m, 1H), 7.43–7.48 (m, 1H),7.39–7.41 (m, 1H), 7.25–7.34 (m, 2H), 6.37 (s, 2H), 5.70 (s, 1H), 3.73 (s, 3H).

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	0.0783 (2)	0.3470 (3)	−0.13490 (12)	0.0803 (8)
O2	0.1384 (3)	0.2208 (3)	−0.22294 (13)	0.0969 (9)
O3	0.4631 (2)	0.1599 (3)	−0.05165 (14)	0.0710 (7)
O4	−0.1041 (2)	0.3351 (4)	0.0420 (2)	0.1180 (12)
O5	−0.1095 (2)	0.1322 (4)	0.11090 (16)	0.0944 (9)
N1	0.3520 (3)	0.0912 (3)	−0.17013 (17)	0.0857 (10)
H1A	0.2888	0.0876	−0.2093	0.103*
H1B	0.4138	0.0438	−0.1720	0.103*
N2	−0.0615 (2)	0.2156 (4)	0.07601 (18)	0.0698 (8)
C1	−0.0358 (4)	0.3802 (6)	−0.1936 (2)	0.1223 (19)
H1C	−0.0840	0.4363	−0.1698	0.183*
H1D	−0.0733	0.2837	−0.2146	0.183*
H1E	−0.0245	0.4421	−0.2346	0.183*
C2	0.1594 (3)	0.2675 (4)	−0.15602 (18)	0.0666 (10)
C3	0.2661 (3)	0.2512 (3)	−0.09329 (16)	0.0537 (8)
C4	0.3544 (3)	0.1709 (4)	−0.10586 (19)	0.0627 (9)
C5	0.4900 (3)	0.2569 (3)	0.01385 (18)	0.0555 (8)
C6	0.6083 (3)	0.2640 (4)	0.0562 (2)	0.0664 (9)
H6A	0.6622	0.2073	0.0404	0.080*
C7	0.6444 (3)	0.3539 (4)	0.1207 (2)	0.0649 (9)
H7A	0.7236	0.3589	0.1490	0.078*
C8	0.5635 (3)	0.4408 (3)	0.14578 (16)	0.0512 (7)
C9	0.5984 (3)	0.5334 (4)	0.21285 (18)	0.0631 (9)
H9A	0.6772	0.5382	0.2422	0.076*
C10	0.5197 (3)	0.6166 (4)	0.23616 (18)	0.0656 (9)
H10A	0.5447	0.6767	0.2812	0.079*
C11	0.4020 (3)	0.6113 (4)	0.19236 (17)	0.0589 (8)
H11A	0.3484	0.6691	0.2080	0.071*
C12	0.3639 (3)	0.5227 (3)	0.12677 (16)	0.0500 (7)
H12A	0.2847	0.5209	0.0984	0.060*
C13	0.4430 (2)	0.4330 (3)	0.10089 (15)	0.0443 (7)
C14	0.4061 (2)	0.3369 (3)	0.03324 (15)	0.0454 (7)
C15	0.2796 (2)	0.3182 (3)	−0.01415 (15)	0.0456 (7)
H15A	0.2434	0.4219	−0.0216	0.055*
C16	0.2153 (2)	0.2162 (3)	0.02856 (14)	0.0420 (6)
C17	0.2586 (3)	0.0694 (3)	0.05726 (16)	0.0499 (7)
H17A	0.3289	0.0353	0.0524	0.060*
C18	0.1991 (3)	−0.0260 (4)	0.09276 (17)	0.0597 (8)
H18A	0.2299	−0.1230	0.1117	0.072*
C19	0.0945 (3)	0.0210 (4)	0.10051 (16)	0.0566 (8)
H19A	0.0536	−0.0425	0.1242	0.068*
C20	0.0529 (2)	0.1659 (4)	0.07174 (16)	0.0502 (7)
C21	0.1104 (2)	0.2630 (3)	0.03579 (16)	0.0491 (7)
H21A	0.0786	0.3594	0.0165	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0909 (18)	0.0813 (17)	0.0520 (13)	0.0104 (15)	0.0000 (13)	0.0034 (12)
O2	0.139 (2)	0.090 (2)	0.0512 (14)	−0.0232 (18)	0.0164 (15)	−0.0123 (13)
O3	0.0914 (18)	0.0486 (13)	0.0870 (16)	0.0073 (12)	0.0485 (15)	−0.0113 (12)
O4	0.0788 (19)	0.0693 (19)	0.223 (4)	0.0214 (16)	0.072 (2)	0.015 (2)
O5	0.0654 (16)	0.128 (2)	0.0994 (19)	−0.0123 (16)	0.0394 (15)	0.0063 (18)
N1	0.136 (3)	0.0588 (18)	0.0772 (19)	−0.0104 (19)	0.0554 (19)	−0.0213 (16)
N2	0.0520 (17)	0.072 (2)	0.088 (2)	−0.0085 (16)	0.0267 (16)	−0.0122 (17)
C1	0.139 (4)	0.106 (4)	0.076 (3)	0.024 (3)	−0.028 (3)	0.018 (3)
C2	0.102 (3)	0.0475 (19)	0.0460 (19)	−0.0165 (19)	0.0182 (19)	−0.0004 (15)
C3	0.075 (2)	0.0394 (16)	0.0487 (16)	−0.0082 (15)	0.0223 (16)	−0.0030 (13)
C4	0.094 (3)	0.0385 (17)	0.060 (2)	−0.0124 (17)	0.032 (2)	−0.0050 (15)
C5	0.068 (2)	0.0400 (16)	0.066 (2)	0.0021 (15)	0.0319 (17)	0.0010 (15)
C6	0.061 (2)	0.053 (2)	0.096 (3)	0.0098 (16)	0.039 (2)	0.0078 (19)
C7	0.0481 (18)	0.061 (2)	0.085 (2)	−0.0021 (16)	0.0196 (17)	0.0174 (19)
C8	0.0542 (18)	0.0423 (16)	0.0556 (17)	−0.0052 (14)	0.0155 (14)	0.0129 (14)
C9	0.062 (2)	0.061 (2)	0.0569 (18)	−0.0144 (17)	0.0061 (16)	0.0102 (16)
C10	0.088 (3)	0.0514 (19)	0.0504 (18)	−0.0150 (18)	0.0123 (18)	−0.0046 (15)
C11	0.078 (2)	0.0470 (18)	0.0521 (17)	−0.0016 (16)	0.0215 (17)	−0.0004 (14)
C12	0.0565 (18)	0.0413 (16)	0.0517 (16)	0.0012 (14)	0.0170 (14)	0.0008 (13)
C13	0.0527 (17)	0.0346 (14)	0.0458 (15)	−0.0009 (13)	0.0163 (13)	0.0082 (12)
C14	0.0557 (17)	0.0322 (14)	0.0522 (16)	0.0016 (13)	0.0228 (14)	0.0054 (12)
C15	0.0559 (17)	0.0318 (14)	0.0491 (16)	0.0030 (13)	0.0171 (13)	0.0022 (12)
C16	0.0468 (16)	0.0330 (14)	0.0425 (14)	0.0002 (12)	0.0095 (12)	−0.0019 (12)
C17	0.0525 (17)	0.0417 (16)	0.0546 (16)	0.0061 (14)	0.0161 (13)	0.0020 (14)
C18	0.067 (2)	0.0446 (18)	0.0615 (19)	0.0047 (16)	0.0132 (16)	0.0134 (15)
C19	0.0603 (19)	0.0559 (19)	0.0521 (17)	−0.0086 (16)	0.0162 (15)	0.0041 (15)
C20	0.0446 (16)	0.0507 (18)	0.0536 (17)	−0.0052 (14)	0.0134 (13)	−0.0063 (14)
C21	0.0504 (17)	0.0374 (15)	0.0560 (17)	0.0027 (13)	0.0125 (14)	−0.0026 (13)

Geometric parameters (Å, º)

O1—C2	1.347 (4)	C8—C13	1.422 (4)
O1—C1	1.473 (4)	C9—C10	1.362 (5)
O2—C2	1.227 (3)	C9—H9A	0.93
O3—C4	1.367 (4)	C10—C11	1.389 (4)
O3—C5	1.401 (4)	C10—H10A	0.93
O4—N2	1.220 (4)	C11—C12	1.362 (4)
O5—N2	1.220 (4)	C11—H11A	0.93
N1—C4	1.346 (4)	C12—C13	1.420 (4)
N1—H1A	0.86	C12—H12A	0.93
N1—H1B	0.86	C13—C14	1.426 (4)
N2—C20	1.473 (4)	C14—C15	1.502 (4)
C1—H1C	0.96	C15—C16	1.536 (4)
C1—H1D	0.96	C15—H15A	0.98
C1—H1E	0.96	C16—C21	1.377 (4)
C2—C3	1.426 (5)	C16—C17	1.396 (4)
C3—C4	1.350 (5)	C17—C18	1.380 (4)
C3—C15	1.508 (4)	C17—H17A	0.93
C5—C14	1.362 (4)	C18—C19	1.378 (4)
C5—C6	1.389 (4)	C18—H18A	0.93
C6—C7	1.351 (5)	C19—C20	1.376 (4)
C6—H6A	0.93	C19—H19A	0.93
C7—C8	1.417 (4)	C20—C21	1.377 (4)
C7—H7A	0.93	C21—H21A	0.93
C8—C9	1.400 (4)
C2—O1—C1	119.2 (3)	C9—C10—H10A	120.2
C4—O3—C5	118.5 (2)	C11—C10—H10A	120.2
C4—N1—H1A	120.0	C12—C11—C10	120.8 (3)
C4—N1—H1B	120.0	C12—C11—H11A	119.6
H1A—N1—H1B	120.0	C10—C11—H11A	119.6
O5—N2—O4	124.1 (3)	C11—C12—C13	121.3 (3)
O5—N2—C20	118.2 (3)	C11—C12—H12A	119.4
O4—N2—C20	117.7 (3)	C13—C12—H12A	119.4
O1—C1—H1C	109.5	C12—C13—C8	117.3 (3)
O1—C1—H1D	109.5	C12—C13—C14	122.8 (2)
H1C—C1—H1D	109.5	C8—C13—C14	119.9 (3)
O1—C1—H1E	109.5	C5—C14—C13	117.6 (3)
H1C—C1—H1E	109.5	C5—C14—C15	120.3 (3)
H1D—C1—H1E	109.5	C13—C14—C15	122.1 (2)
O2—C2—O1	120.8 (3)	C14—C15—C3	111.2 (2)
O2—C2—C3	127.1 (4)	C14—C15—C16	111.0 (2)
O1—C2—C3	112.1 (3)	C3—C15—C16	110.5 (2)
C4—C3—C2	118.4 (3)	C14—C15—H15A	108.0
C4—C3—C15	120.6 (3)	C3—C15—H15A	108.0
C2—C3—C15	121.0 (3)	C16—C15—H15A	108.0
N1—C4—C3	127.6 (4)	C21—C16—C17	118.1 (3)
N1—C4—O3	109.6 (3)	C21—C16—C15	121.0 (2)
C3—C4—O3	122.8 (3)	C17—C16—C15	120.7 (2)
C14—C5—C6	123.6 (3)	C18—C17—C16	121.2 (3)
C14—C5—O3	122.1 (3)	C18—C17—H17A	119.4
C6—C5—O3	114.3 (3)	C16—C17—H17A	119.4
C7—C6—C5	119.4 (3)	C19—C18—C17	120.7 (3)
C7—C6—H6A	120.3	C19—C18—H18A	119.6
C5—C6—H6A	120.3	C17—C18—H18A	119.6
C6—C7—C8	121.0 (3)	C20—C19—C18	117.3 (3)
C6—C7—H7A	119.5	C20—C19—H19A	121.3
C8—C7—H7A	119.5	C18—C19—H19A	121.3
C9—C8—C7	122.2 (3)	C19—C20—C21	123.1 (3)
C9—C8—C13	119.4 (3)	C19—C20—N2	118.3 (3)
C7—C8—C13	118.5 (3)	C21—C20—N2	118.6 (3)
C10—C9—C8	121.5 (3)	C16—C21—C20	119.5 (3)
C10—C9—H9A	119.2	C16—C21—H21A	120.2
C8—C9—H9A	119.2	C20—C21—H21A	120.2
C9—C10—C11	119.6 (3)
C1—O1—C2—O2	−1.2 (5)	C6—C5—C14—C15	−177.8 (3)
C1—O1—C2—C3	177.5 (3)	O3—C5—C14—C15	2.4 (4)
O2—C2—C3—C4	−2.8 (5)	C12—C13—C14—C5	179.6 (2)
O1—C2—C3—C4	178.6 (3)	C8—C13—C14—C5	−0.8 (4)
O2—C2—C3—C15	178.7 (3)	C12—C13—C14—C15	−2.6 (4)
O1—C2—C3—C15	0.1 (4)	C8—C13—C14—C15	177.0 (2)
C2—C3—C4—N1	−5.8 (5)	C5—C14—C15—C3	−18.8 (4)
C15—C3—C4—N1	172.7 (3)	C13—C14—C15—C3	163.5 (2)
C2—C3—C4—O3	174.4 (3)	C5—C14—C15—C16	104.8 (3)
C15—C3—C4—O3	−7.2 (5)	C13—C14—C15—C16	−73.0 (3)
C5—O3—C4—N1	168.8 (2)	C4—C3—C15—C14	21.3 (4)
C5—O3—C4—C3	−11.3 (4)	C2—C3—C15—C14	−160.3 (3)
C4—O3—C5—C14	13.8 (4)	C4—C3—C15—C16	−102.5 (3)
C4—O3—C5—C6	−166.1 (3)	C2—C3—C15—C16	75.9 (3)
C14—C5—C6—C7	0.3 (5)	C14—C15—C16—C21	131.4 (3)
O3—C5—C6—C7	−179.9 (3)	C3—C15—C16—C21	−104.7 (3)
C5—C6—C7—C8	0.1 (5)	C14—C15—C16—C17	−52.3 (3)
C6—C7—C8—C9	179.2 (3)	C3—C15—C16—C17	71.6 (3)
C6—C7—C8—C13	−0.8 (4)	C21—C16—C17—C18	−0.8 (4)
C7—C8—C9—C10	179.8 (3)	C15—C16—C17—C18	−177.2 (2)
C13—C8—C9—C10	−0.1 (4)	C16—C17—C18—C19	0.3 (4)
C8—C9—C10—C11	−0.6 (5)	C17—C18—C19—C20	−0.2 (4)
C9—C10—C11—C12	0.7 (5)	C18—C19—C20—C21	0.5 (4)
C10—C11—C12—C13	−0.1 (4)	C18—C19—C20—N2	177.1 (3)
C11—C12—C13—C8	−0.6 (4)	O5—N2—C20—C19	6.3 (4)
C11—C12—C13—C14	179.0 (3)	O4—N2—C20—C19	−171.1 (3)
C9—C8—C13—C12	0.7 (4)	O5—N2—C20—C21	−176.8 (3)
C7—C8—C13—C12	−179.2 (2)	O4—N2—C20—C21	5.7 (4)
C9—C8—C13—C14	−178.9 (2)	C17—C16—C21—C20	1.0 (4)
C7—C8—C13—C14	1.2 (4)	C15—C16—C21—C20	177.4 (2)
C6—C5—C14—C13	0.1 (4)	C19—C20—C21—C16	−0.9 (4)
O3—C5—C14—C13	−179.7 (2)	N2—C20—C21—C16	−177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.09	2.687 (5)	126