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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o775.
Published online 2009 March 14. doi:  10.1107/S1600536809008885
PMCID: PMC2969098

Ethyl 3-amino-1-phenyl-1H-benzo[f]chromene-2-carboxyl­ate

Abstract

The pyranyl ring of the title compound, C22H19NO3, adopts a flattened-boat conformation. The dihedral angle between naphthalene and phenyl rings is 78.3 (1)°The mol­ecule also features an intra­molecular N—H(...)Ocarbon­yl hydrogen bond. Adjacent mol­ecules are linked by an inter­molecular N—H(...)Ocarbon­yl hydrogen bond, forming a zigzag chain that runs along the c axis.

Related literature

For the crystal structures of other ethyl 3-amino-1-aryl-1H-benzo[f]chromene-2-carboxyl­ate derivatives, see: Klokol et al. (1987 [triangle]); Shi et al. (2003a [triangle],b [triangle]); Wang et al. (2003 [triangle]); Zhuang et al. (2003a [triangle],b [triangle]).

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Object name is e-65-0o775-scheme1.jpg

Experimental

Crystal data

  • C22H19NO3
  • M r = 345.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o775-efi1.jpg
  • a = 13.7835 (5) Å
  • b = 14.6460 (4) Å
  • c = 8.8713 (2) Å
  • β = 99.551 (1)°
  • V = 1766.05 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 153 K
  • 0.36 × 0.25 × 0.14 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.864, T max = 0.988
  • 8563 measured reflections
  • 2029 independent reflections
  • 1958 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.078
  • S = 1.09
  • 2029 reflections
  • 244 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008885/zl2186sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008885/zl2186Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Huangshi Institute of Technology (grant No. 08yjz23B) and the University of Malaya for supporting this work.

supplementary crystallographic information

Comment

2-Naphthol, substituted benzaldehydes and ethyl 2-cyanoacetate react in the presence of a catalyst to form the ethyl 3-amino-1-aryl-1H-benzo[f]chromene-2-carboxylates; the compounds possess a primary amine group. The crystal structures of several 1-aryl derivatives have been reported (Klokol et al., 1987; Shi et al., 2003a; Shi et al., 2003b; Wang et al., 2003; Zhuang et al., 2003a; Zhuang et al., 2003b). Interestingly, the crystal structure of the unsubstituted 1-phenyl compound was not known, and its structure is reported here. The title compound (Scheme I, Fig. 1) exhibits a pyranyl ring in a flattened boat conformation. The molecule also features an intramolecular NH···Ocarbonyl bond. Adjacent molecules are linked by an intermolecular N—H···Ocarbonyl hydrogen bond to furnish a zigzag chain that runs along the c-axis.

Experimental

2-Naphthol (1.4 g, 10 mmol), benzaldehyde (1.1 g, 10 mmol), ethyl 2-cyanoacetate (1.0 g, 10 mmol) and piperidine (1 ml) were dissolved in ethanol (30 ml). The solution was heated for 5 h. The solvent was removed under reduced pressure and and the residue recrystallized from dichloromethane/methanol (1:1/v:v) to give yellow crystals in 80% yield; m.p. 436–437 K.

Refinement

In the absence of significant anomalous scattering Friedel pairs were merged prior to refinement and the absolute configuration of the molecule was not refined. Carbon-bound H atoms were placed in calculated positions [C—H 0.95–1.00 Å and Uiso(H) 1.2–1.5Ueq(C)], and were included in the refinement in the riding-model approximation. The amino H-atoms were located in a difference Fourier map, and were refined with an N–H distance restraint of 0.88 (1) Å; their isotropic temperature factures were refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C22H19NO3; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius.
Fig. 2.
Thermal ellipsoid plot (Barbour, 2001) showing the intra and intermolecular hydrogen bonding interactions (dashed lines); displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius.

Crystal data

C22H19NO3F(000) = 728
Mr = 345.38Dx = 1.299 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 8058 reflections
a = 13.7835 (5) Åθ = 3.0–27.5°
b = 14.6460 (4) ŵ = 0.09 mm1
c = 8.8713 (2) ÅT = 153 K
β = 99.551 (1)°Block, yellow
V = 1766.05 (9) Å30.36 × 0.25 × 0.14 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2029 independent reflections
Radiation source: fine-focus sealed tube1958 reflections with I > 2σ(I)
graphiteRint = 0.016
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −18→18
Tmin = 0.864, Tmax = 0.988l = −10→11
8563 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0522P)2 + 0.3553P] where P = (Fo2 + 2Fc2)/3
2029 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.19 e Å3
4 restraintsΔρmin = −0.27 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.50000 (10)0.89966 (8)0.50000 (13)0.0251 (3)
O20.57192 (9)0.73346 (8)0.07916 (12)0.0221 (3)
O30.57203 (10)0.88667 (8)0.05998 (13)0.0243 (3)
N10.54563 (13)0.98073 (10)0.31277 (17)0.0289 (3)
H110.5480 (18)1.0271 (12)0.376 (2)0.038 (7)*
H120.5641 (18)0.9858 (18)0.2234 (17)0.040 (7)*
C10.53026 (11)0.72524 (11)0.36834 (17)0.0176 (3)
H10.49680.68100.29080.021*
C20.63064 (12)0.68559 (10)0.43558 (18)0.0199 (3)
C30.66322 (13)0.60409 (11)0.3813 (2)0.0254 (4)
H30.62280.57280.30040.031*
C40.75447 (14)0.56763 (13)0.4441 (3)0.0335 (4)
H40.77590.51180.40600.040*
C50.81378 (14)0.61264 (14)0.5619 (3)0.0364 (5)
H50.87560.58740.60560.044*
C60.78287 (14)0.69460 (15)0.6159 (2)0.0357 (5)
H60.82390.72600.69590.043*
C70.69180 (13)0.73093 (13)0.5532 (2)0.0276 (4)
H70.67110.78710.59080.033*
C80.46549 (12)0.73777 (11)0.48933 (17)0.0191 (3)
C90.41664 (12)0.66266 (12)0.54835 (17)0.0204 (3)
C100.43046 (13)0.57101 (12)0.50594 (18)0.0247 (3)
H100.47320.55800.43490.030*
C110.38294 (15)0.50035 (13)0.5660 (2)0.0305 (4)
H11A0.39410.43920.53780.037*
C120.31800 (14)0.51858 (14)0.6691 (2)0.0322 (4)
H12A0.28400.46980.70790.039*
C130.30372 (14)0.60584 (14)0.7134 (2)0.0297 (4)
H130.26010.61720.78370.036*
C140.35287 (12)0.68005 (13)0.65636 (19)0.0240 (4)
C150.34044 (13)0.77096 (13)0.7054 (2)0.0278 (4)
H150.29740.78270.77640.033*
C160.38932 (14)0.84127 (13)0.65223 (19)0.0262 (4)
H160.38160.90180.68670.031*
C170.45205 (12)0.82298 (12)0.54462 (18)0.0217 (3)
C180.53012 (12)0.89655 (11)0.36102 (17)0.0213 (3)
C190.53928 (12)0.81562 (10)0.28807 (18)0.0186 (3)
C200.56246 (12)0.81763 (10)0.13523 (18)0.0185 (3)
C210.59893 (13)0.72831 (11)−0.07209 (18)0.0239 (3)
H21A0.66440.7561−0.07170.029*
H21B0.55020.7611−0.14750.029*
C220.60081 (17)0.62865 (13)−0.1116 (2)0.0336 (4)
H22A0.53450.6031−0.11830.050*
H22B0.64590.5964−0.03210.050*
H22C0.62320.6214−0.21010.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0364 (7)0.0209 (6)0.0193 (5)−0.0010 (5)0.0086 (5)−0.0031 (4)
O20.0328 (6)0.0182 (5)0.0168 (5)0.0025 (5)0.0084 (4)0.0014 (4)
O30.0334 (7)0.0200 (6)0.0199 (5)0.0007 (5)0.0059 (5)0.0027 (4)
N10.0473 (9)0.0188 (7)0.0216 (7)−0.0023 (6)0.0088 (6)−0.0033 (6)
C10.0189 (7)0.0185 (7)0.0156 (6)0.0004 (5)0.0036 (5)0.0004 (5)
C20.0194 (7)0.0223 (7)0.0190 (7)−0.0004 (6)0.0061 (5)0.0069 (6)
C30.0223 (8)0.0188 (7)0.0357 (10)−0.0010 (6)0.0060 (7)0.0053 (6)
C40.0243 (8)0.0223 (8)0.0553 (12)0.0029 (7)0.0108 (8)0.0109 (8)
C50.0202 (8)0.0387 (11)0.0489 (12)0.0022 (7)0.0012 (8)0.0183 (9)
C60.0245 (9)0.0507 (12)0.0298 (9)−0.0019 (8)−0.0014 (7)0.0060 (8)
C70.0236 (8)0.0359 (9)0.0230 (8)−0.0006 (7)0.0026 (6)0.0006 (7)
C80.0187 (7)0.0215 (7)0.0168 (7)0.0006 (6)0.0024 (6)0.0015 (6)
C90.0187 (7)0.0267 (8)0.0155 (6)−0.0001 (6)0.0017 (5)0.0015 (6)
C100.0279 (8)0.0250 (8)0.0221 (8)−0.0044 (6)0.0067 (6)0.0003 (6)
C110.0365 (10)0.0277 (8)0.0272 (9)−0.0071 (8)0.0053 (7)0.0014 (7)
C120.0309 (9)0.0365 (10)0.0296 (9)−0.0103 (7)0.0059 (7)0.0065 (8)
C130.0225 (8)0.0440 (10)0.0239 (8)−0.0020 (7)0.0078 (6)0.0057 (7)
C140.0190 (7)0.0320 (9)0.0208 (8)0.0011 (6)0.0030 (6)0.0024 (6)
C150.0241 (8)0.0376 (10)0.0233 (8)0.0063 (7)0.0085 (6)−0.0007 (7)
C160.0277 (8)0.0276 (9)0.0240 (8)0.0056 (7)0.0063 (7)−0.0033 (7)
C170.0228 (8)0.0251 (8)0.0173 (7)0.0017 (6)0.0031 (6)0.0007 (6)
C180.0254 (8)0.0226 (8)0.0153 (7)0.0002 (6)0.0020 (6)0.0005 (6)
C190.0206 (7)0.0177 (7)0.0169 (7)0.0001 (5)0.0016 (6)0.0018 (5)
C200.0199 (7)0.0173 (7)0.0180 (7)0.0018 (5)0.0021 (5)0.0012 (5)
C210.0330 (9)0.0233 (8)0.0173 (8)0.0011 (7)0.0092 (6)−0.0003 (6)
C220.0519 (11)0.0238 (8)0.0280 (9)0.0062 (8)0.0155 (8)−0.0017 (7)

Geometric parameters (Å, °)

O1—C181.3654 (19)C8—C91.433 (2)
O1—C171.393 (2)C9—C101.415 (2)
O2—C201.3437 (19)C9—C141.427 (2)
O2—C211.4527 (18)C10—C111.378 (2)
O3—C201.231 (2)C10—H100.9500
N1—C181.334 (2)C11—C121.407 (3)
N1—H110.876 (10)C11—H11A0.9500
N1—H120.875 (10)C12—C131.361 (3)
C1—C81.517 (2)C12—H12A0.9500
C1—C191.518 (2)C13—C141.418 (3)
C1—C21.528 (2)C13—H130.9500
C1—H11.0000C14—C151.420 (3)
C2—C31.389 (2)C15—C161.357 (3)
C2—C71.396 (2)C15—H150.9500
C3—C41.395 (2)C16—C171.416 (2)
C3—H30.9500C16—H160.9500
C4—C51.382 (3)C18—C191.366 (2)
C4—H40.9500C19—C201.444 (2)
C5—C61.386 (3)C21—C221.502 (2)
C5—H50.9500C21—H21A0.9900
C6—C71.392 (3)C21—H21B0.9900
C6—H60.9500C22—H22A0.9800
C7—H70.9500C22—H22B0.9800
C8—C171.365 (2)C22—H22C0.9800
C18—O1—C17117.34 (13)C12—C11—H11A119.9
C20—O2—C21116.42 (12)C13—C12—C11120.25 (17)
C18—N1—H11120.2 (17)C13—C12—H12A119.9
C18—N1—H12117.1 (17)C11—C12—H12A119.9
H11—N1—H12122 (2)C12—C13—C14121.08 (17)
C8—C1—C19109.27 (13)C12—C13—H13119.5
C8—C1—C2111.78 (13)C14—C13—H13119.5
C19—C1—C2112.04 (12)C13—C14—C15121.35 (16)
C8—C1—H1107.9C13—C14—C9119.15 (16)
C19—C1—H1107.9C15—C14—C9119.50 (15)
C2—C1—H1107.9C16—C15—C14120.85 (16)
C3—C2—C7118.56 (15)C16—C15—H15119.6
C3—C2—C1121.00 (14)C14—C15—H15119.6
C7—C2—C1120.44 (15)C15—C16—C17118.99 (16)
C2—C3—C4120.82 (17)C15—C16—H16120.5
C2—C3—H3119.6C17—C16—H16120.5
C4—C3—H3119.6C8—C17—O1122.40 (14)
C5—C4—C3120.03 (18)C8—C17—C16123.36 (16)
C5—C4—H4120.0O1—C17—C16114.24 (14)
C3—C4—H4120.0N1—C18—O1110.36 (14)
C4—C5—C6119.83 (17)N1—C18—C19128.13 (15)
C4—C5—H5120.1O1—C18—C19121.50 (14)
C6—C5—H5120.1C18—C19—C20118.64 (14)
C5—C6—C7120.10 (18)C18—C19—C1120.87 (14)
C5—C6—H6120.0C20—C19—C1120.42 (13)
C7—C6—H6120.0O3—C20—O2121.82 (15)
C6—C7—C2120.65 (18)O3—C20—C19125.89 (14)
C6—C7—H7119.7O2—C20—C19112.28 (13)
C2—C7—H7119.7O2—C21—C22106.43 (13)
C17—C8—C9118.06 (14)O2—C21—H21A110.4
C17—C8—C1119.73 (14)C22—C21—H21A110.4
C9—C8—C1122.20 (14)O2—C21—H21B110.4
C10—C9—C14118.23 (15)C22—C21—H21B110.4
C10—C9—C8122.59 (15)H21A—C21—H21B108.6
C14—C9—C8119.17 (15)C21—C22—H22A109.5
C11—C10—C9121.04 (16)C21—C22—H22B109.5
C11—C10—H10119.5H22A—C22—H22B109.5
C9—C10—H10119.5C21—C22—H22C109.5
C10—C11—C12120.21 (18)H22A—C22—H22C109.5
C10—C11—H11A119.9H22B—C22—H22C109.5
C8—C1—C2—C3121.86 (16)C8—C9—C14—C15−1.2 (2)
C19—C1—C2—C3−115.10 (16)C13—C14—C15—C16178.73 (17)
C8—C1—C2—C7−58.27 (19)C9—C14—C15—C16−0.8 (3)
C19—C1—C2—C764.76 (19)C14—C15—C16—C171.0 (3)
C7—C2—C3—C40.8 (2)C9—C8—C17—O1176.85 (14)
C1—C2—C3—C4−179.31 (16)C1—C8—C17—O1−3.5 (2)
C2—C3—C4—C50.0 (3)C9—C8—C17—C16−2.7 (2)
C3—C4—C5—C6−0.8 (3)C1—C8—C17—C16176.99 (16)
C4—C5—C6—C70.8 (3)C18—O1—C17—C824.8 (2)
C5—C6—C7—C20.0 (3)C18—O1—C17—C16−155.62 (15)
C3—C2—C7—C6−0.8 (3)C15—C16—C17—C80.8 (3)
C1—C2—C7—C6179.31 (16)C15—C16—C17—O1−178.81 (15)
C19—C1—C8—C17−20.86 (19)C17—O1—C18—N1160.53 (15)
C2—C1—C8—C17103.73 (16)C17—O1—C18—C19−18.3 (2)
C19—C1—C8—C9158.81 (13)N1—C18—C19—C20−4.4 (3)
C2—C1—C8—C9−76.60 (18)O1—C18—C19—C20174.24 (15)
C17—C8—C9—C10−175.95 (15)N1—C18—C19—C1172.70 (16)
C1—C8—C9—C104.4 (2)O1—C18—C19—C1−8.7 (2)
C17—C8—C9—C142.8 (2)C8—C1—C19—C1827.1 (2)
C1—C8—C9—C14−176.84 (15)C2—C1—C19—C18−97.31 (17)
C14—C9—C10—C110.6 (2)C8—C1—C19—C20−155.85 (14)
C8—C9—C10—C11179.41 (15)C2—C1—C19—C2079.71 (17)
C9—C10—C11—C121.2 (3)C21—O2—C20—O33.0 (2)
C10—C11—C12—C13−1.8 (3)C21—O2—C20—C19−177.75 (13)
C11—C12—C13—C140.5 (3)C18—C19—C20—O3−2.5 (2)
C12—C13—C14—C15−178.19 (18)C1—C19—C20—O3−179.59 (16)
C12—C13—C14—C91.3 (3)C18—C19—C20—O2178.28 (15)
C10—C9—C14—C13−1.9 (2)C1—C19—C20—O21.20 (19)
C8—C9—C14—C13179.31 (15)C20—O2—C21—C22−177.74 (14)
C10—C9—C14—C15177.66 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H11···O3i0.88 (1)2.05 (1)2.907 (2)166 (2)
N1—H12···O30.88 (1)2.07 (2)2.707 (2)129 (2)

Symmetry codes: (i) x, −y+2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2186).

References

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  • Shi, D.-Q., Wang, J., Wang, X., Zhuang, Q. & Yu, K. (2003a). Acta Cryst. E59, o1733–o1734.
  • Shi, D., Wu, H., Wang, X., Zhuang, Q. & Hu, H. (2003b). Acta Cryst. E59, o1263–o1264.
  • Wang, X.-S., Shi, D.-Q. & Tu, S.-J. (2003). Chin. J. Chem.21, 1114–1117.
  • Westrip, S. P. (2009). publCIF In preparation.
  • Zhuang, Q.-Y., Rong, L.-C., Wang, J.-X., Tu, S.-J., Wang, X.-S. & Shi, D.-Q. (2003a). Chin. J. Org. Chem.23, 671–673.
  • Zhuang, Q.-Y., Zhang, S., Shi, D.-Q., Tu, S.-J. & Wang, X.-S. (2003b). J. Xuzhou Normal Univ. (Natur. Sci.), 21, 49–52.

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