organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Methyl 4-benz­yl­oxy-7-meth­­oxy-1-methyl-1H-indole-2-carboxyl­ate

aSchool of Pharmaceutical Sciences, Shandong University, Jinan 250012, People's Republic of China
*Correspondence e-mail: guisenzhao@sdu.edu.cn

(Received 12 March 2012; accepted 9 July 2012; online 18 July 2012)

There are two independent mol­ecules in the asymmetric unit of the title compound, C19H19NO4. The indole unit in each mol­ecule is essentially planar, with mean deviations of 0.017 (1) and 0.013 (1) Å and forms dihedral angles of 50.17 (7) and 26.05 (6)° with the phenyl ring. In the crystal, mol­ecules are linked by weak C–H⋯π inter­actions.

Related literature

For the anti­tumor activity of substituted indole compounds, see: Ziedan et al. (2010[Ziedan, N. I., Stefanelli, F., Fogli, S. & Westwell, A. D. (2010). Eur. J. Med. Chem. 45, 4523-4530.]). For the crystal structures of related compounds, see: Butcher et al. (2006[Butcher, R. J., Yathirajan, H. S., Ashalatha, B. V., Narayana, B. & Sarojini, B. K. (2006). Acta Cryst. E62, o3915-o3917.], 2007[Butcher, R. J., Jasinski, J. P., Yathirajan, H. S., Ashalatha, B. V. & Narayana, B. (2007). Acta Cryst. E63, o3505.]); Harrison et al. (2006[Harrison, W. T. A., Yathirajan, H. S., Ashalatha, B. V., Vijaya Raj, K. K. & Narayana, B. (2006). Acta Cryst. E62, o4050-o4051.]); Hu et al. (2005[Hu, S.-C., Tan, R.-X., Hong, K., Yu, Z.-N. & Zhu, H.-L. (2005). Acta Cryst. E61, o1654-o1656.]). For the synthesis of 5-benz­yloxy-7-bromo-1H-indole-2-carb­oxy­lic acid, see: Fresneda et al.(2001[Fresneda, P. M., Molinap, P. & Bleda, J. A. (2001). Tetrahedron, 57, 2355-2363.]).

[Scheme 1]

Experimental

Crystal data
  • C19H19NO4

  • Mr = 325.35

  • Triclinic, [P \overline 1]

  • a = 7.622 (2) Å

  • b = 12.871 (4) Å

  • c = 16.928 (5) Å

  • α = 93.831 (3)°

  • β = 100.158 (3)°

  • γ = 93.456 (3)°

  • V = 1626.6 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.38 × 0.36 × 0.25 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. ]) Tmin = 0.965, Tmax = 0.977

  • 19234 measured reflections

  • 7421 independent reflections

  • 5286 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.134

  • S = 1.05

  • 7421 reflections

  • 440 parameters

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C20–C25 phenyl, C1–C6 phenyl, C27–C32 phenyl and C12–C15/N1 pyrrole rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C5—H5⋯Cg1 0.93 2.88 3.6778 (7) 145
C16—H16ACg2i 0.96 2.87 3.7812 (9) 158
C17—H17CCg3ii 0.96 2.90 3.845 (1) 167
C26—H26ACg4iii 0.96 2.94 3.7442 (8) 141
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y, z.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. ]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. ]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2008[Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Substituted indole derivatives have attracted much attention due to their biological properties such as antitumor activities (Ziedan et al. 2010). Recently, the crystal structures of methyl 5-halo-1H-indole-2-carboxylate analogues were reported (Butcher et al., 2006, 2007; Harrison et al., 2006). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. There are two independent unique molecules [labelled A & B] in which the indole unit is essentially planar, with mean deviations of 0.017 (1) Å for A and 0.013 (1) Å for B, respectively, from the least-squares plane defined by the nine constituent atoms. The crystal packing is stabilized by weak intermolecular C–H···π interactions (Table 1 & Fig. 2, Cg1, Cg2, Cg3 and Cg4 are the centroids of C20-C25 pheny ring, C1-C6 pheny ring, C27-C32 pheny ring and C12-C15/N1 pyrrol ring, respectively.

Related literature top

For the antitumor activity of substituted indole compounds, see: Ziedan et al. (2010). For the crystal structures of related compounds, see: Butcher et al. (2006, 2007); Harrison et al. (2006); Hu et al. (2005). For the synthesis of 5-benzyloxy-7-bromo-1H-indole-2-carboxylic acid, see: Fresneda et al.(2001).

Experimental top

A mixture of 4-(benzyloxy)-7-bromo-1H-indole-2-carboxylic acid (Fresneda et al., 2001) (0.35 g, 1 mmol), CuI (0.19 g, 1 mmol), CH3ONa (0.38 g, 7 mmol) in anhydrous CH3OH (2 ml) and DMF (4 ml) under N2 atmosphere was heated to reflux for 5 h. After cooling to r.t., the mixture was poured into water (50 ml) and acidified with aq. HCl (6 N) to pH 1-2. The precipitate was filtered, washed several times with water, dried under vacuum, and then dissolved in anhydrous DMF. NaH (0.04 g, 1.5 mmol) was added to the solution under 0 oC followed by dimethyl sulfate (0.19 g, 1.5 mmol). The mixture was stired at r.t. for 4 h, and then was poured into ice-cold water. The precipitate was filtered, washed several times with water, and further purified by column chromatography (10% EtOAc/ Petroleum ether) and recrystallization from 10% EtOAc/Petroleum ether gave 0.21 g (64%) of white crystals. Crystals of X-ray diffraction quality were obtained by recrystallization from CH2Cl2/n-hexane mixture (4:1).

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms with C–H = 0.96 Å (methyl) or 0.93 Å (aromatic and methenyl), 0.82 Å (hydroxyl) and Uiso(H) = 1.2Ueq(C or O).

Structure description top

Substituted indole derivatives have attracted much attention due to their biological properties such as antitumor activities (Ziedan et al. 2010). Recently, the crystal structures of methyl 5-halo-1H-indole-2-carboxylate analogues were reported (Butcher et al., 2006, 2007; Harrison et al., 2006). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. There are two independent unique molecules [labelled A & B] in which the indole unit is essentially planar, with mean deviations of 0.017 (1) Å for A and 0.013 (1) Å for B, respectively, from the least-squares plane defined by the nine constituent atoms. The crystal packing is stabilized by weak intermolecular C–H···π interactions (Table 1 & Fig. 2, Cg1, Cg2, Cg3 and Cg4 are the centroids of C20-C25 pheny ring, C1-C6 pheny ring, C27-C32 pheny ring and C12-C15/N1 pyrrol ring, respectively.

For the antitumor activity of substituted indole compounds, see: Ziedan et al. (2010). For the crystal structures of related compounds, see: Butcher et al. (2006, 2007); Harrison et al. (2006); Hu et al. (2005). For the synthesis of 5-benzyloxy-7-bromo-1H-indole-2-carboxylic acid, see: Fresneda et al.(2001).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. A view of the C–H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroids. [Symmetrycodes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y, z.]
Methyl 4-benzyloxy-7-methoxy-1-methyl-1H-indole-2-carboxylate top
Crystal data top
C19H19NO4Z = 4
Mr = 325.35F(000) = 688
Triclinic, P1Dx = 1.329 Mg m3
Hall symbol: -P 1Melting point = 373.1–374.8 K
a = 7.622 (2) ÅMo Kα radiation, λ = 0.71069 Å
b = 12.871 (4) ÅCell parameters from 6012 reflections
c = 16.928 (5) Åθ = 2.5–27.2°
α = 93.831 (3)°µ = 0.09 mm1
β = 100.158 (3)°T = 293 K
γ = 93.456 (3)°Block, colourless
V = 1626.6 (8) Å30.38 × 0.36 × 0.25 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
7421 independent reflections
Radiation source: fine-focus sealed tube5286 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ and ω scansθmax = 27.7°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 99
Tmin = 0.965, Tmax = 0.977k = 1616
19234 measured reflectionsl = 2122
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0655P)2 + 0.2116P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
7421 reflectionsΔρmax = 0.24 e Å3
440 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0035 (9)
Crystal data top
C19H19NO4γ = 93.456 (3)°
Mr = 325.35V = 1626.6 (8) Å3
Triclinic, P1Z = 4
a = 7.622 (2) ÅMo Kα radiation
b = 12.871 (4) ŵ = 0.09 mm1
c = 16.928 (5) ÅT = 293 K
α = 93.831 (3)°0.38 × 0.36 × 0.25 mm
β = 100.158 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
7421 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
5286 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.977Rint = 0.023
19234 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.05Δρmax = 0.24 e Å3
7421 reflectionsΔρmin = 0.17 e Å3
440 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å2) top
xyzUiso*/Ueq
C10.3201 (2)0.71878 (13)0.71353 (9)0.0534 (4)
H10.24740.66260.72400.064*
C20.3716 (3)0.80075 (15)0.77138 (10)0.0667 (5)
H20.33440.79920.82080.080*
C30.4770 (3)0.88439 (14)0.75641 (11)0.0694 (5)
H30.51130.93960.79550.083*
C40.5321 (3)0.88654 (14)0.68313 (11)0.0650 (5)
H40.60290.94360.67270.078*
C50.4826 (2)0.80460 (12)0.62552 (9)0.0544 (4)
H50.52100.80630.57640.065*
C60.37566 (19)0.71944 (11)0.64011 (8)0.0443 (3)
C70.3246 (2)0.62797 (12)0.57930 (8)0.0493 (4)
H7A0.42150.58200.58250.059*
H7B0.21980.58880.59010.059*
C80.23533 (19)0.59066 (11)0.43789 (8)0.0437 (3)
C90.2426 (2)0.48538 (12)0.44087 (9)0.0511 (4)
H90.28430.45820.48970.061*
C100.1877 (2)0.41722 (11)0.37112 (9)0.0505 (4)
H100.19680.34590.37490.061*
C110.12125 (19)0.45221 (10)0.29780 (8)0.0423 (3)
C120.10795 (17)0.56092 (10)0.29461 (8)0.0385 (3)
C130.16855 (18)0.63004 (10)0.36340 (8)0.0396 (3)
C140.14128 (19)0.73230 (11)0.34046 (8)0.0434 (3)
H140.16980.79390.37340.052*
C150.06500 (19)0.72338 (11)0.26068 (8)0.0427 (3)
C160.1099 (3)0.28331 (12)0.23069 (10)0.0602 (4)
H16A0.23710.28120.24500.090*
H16B0.06870.24690.17870.090*
H16C0.05360.25050.27000.090*
C170.0428 (2)0.57773 (12)0.15155 (8)0.0530 (4)
H17A0.00890.50810.14150.079*
H17B0.00710.62120.11240.079*
H17C0.17000.57640.14780.079*
C180.0067 (2)0.80779 (12)0.21026 (9)0.0494 (4)
C190.0144 (4)0.98951 (14)0.21080 (13)0.0948 (8)
H19A0.03850.99290.16350.142*
H19B0.02191.05190.24560.142*
H19C0.14230.98330.19550.142*
C200.8907 (2)0.78348 (12)0.49954 (9)0.0503 (4)
H200.94940.72220.50120.060*
C210.9458 (2)0.86294 (13)0.55865 (9)0.0571 (4)
H211.03980.85450.60040.069*
C220.8629 (2)0.95491 (14)0.55648 (10)0.0606 (4)
H220.90031.00870.59650.073*
C230.7236 (2)0.96653 (14)0.49423 (11)0.0623 (4)
H230.66811.02890.49190.075*
C240.6664 (2)0.88617 (13)0.43554 (10)0.0567 (4)
H240.57140.89450.39430.068*
C250.74889 (19)0.79327 (12)0.43736 (8)0.0463 (3)
C260.6865 (2)0.70257 (12)0.37704 (9)0.0519 (4)
H26A0.78480.65940.37270.062*
H26B0.59280.66040.39440.062*
C270.5479 (2)0.66508 (12)0.24058 (8)0.0466 (3)
C280.5498 (2)0.55956 (12)0.24361 (9)0.0527 (4)
H280.60480.53230.29050.063*
C290.4701 (2)0.49140 (12)0.17701 (9)0.0529 (4)
H290.47470.41990.18110.064*
C300.3858 (2)0.52585 (11)0.10641 (9)0.0478 (3)
C310.38111 (19)0.63503 (11)0.10291 (8)0.0432 (3)
C320.46230 (19)0.70394 (11)0.16862 (8)0.0438 (3)
C330.4334 (2)0.80607 (12)0.14658 (9)0.0482 (3)
H330.47310.86770.17820.058*
C340.3362 (2)0.79755 (11)0.06999 (8)0.0466 (3)
C350.3145 (3)0.35453 (13)0.04259 (11)0.0668 (5)
H35A0.43760.33880.05390.100*
H35B0.25790.31970.00820.100*
H35C0.25490.33110.08430.100*
C360.1910 (3)0.65126 (14)0.03299 (10)0.0663 (5)
H36A0.24830.59580.05660.099*
H36B0.17350.70540.06930.099*
H36C0.07740.62480.02270.099*
C370.2737 (2)0.88262 (12)0.02112 (9)0.0518 (4)
C380.2686 (3)1.06634 (14)0.02114 (13)0.0808 (6)
H38A0.30721.06310.02990.121*
H38B0.32421.12780.05330.121*
H38C0.14111.06890.01280.121*
N10.04466 (15)0.61930 (9)0.23182 (6)0.0408 (3)
N20.30332 (16)0.69353 (9)0.04256 (7)0.0461 (3)
O10.28763 (15)0.66482 (8)0.50106 (6)0.0538 (3)
O20.06565 (15)0.38876 (7)0.22827 (6)0.0517 (3)
O30.06518 (19)0.79859 (9)0.14086 (7)0.0740 (4)
O40.0436 (2)0.90008 (8)0.25245 (7)0.0729 (4)
O50.62046 (16)0.73933 (8)0.30083 (6)0.0570 (3)
O60.30467 (18)0.46313 (9)0.03939 (7)0.0664 (3)
O70.1933 (2)0.87380 (10)0.04683 (7)0.0833 (4)
O80.31871 (19)0.97476 (9)0.06225 (7)0.0706 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0610 (9)0.0577 (9)0.0429 (8)0.0109 (7)0.0091 (7)0.0090 (7)
C20.0911 (13)0.0698 (12)0.0413 (9)0.0209 (10)0.0138 (8)0.0030 (8)
C30.0982 (14)0.0530 (10)0.0510 (10)0.0162 (10)0.0025 (9)0.0069 (8)
C40.0822 (12)0.0496 (9)0.0588 (10)0.0031 (8)0.0005 (9)0.0087 (8)
C50.0671 (10)0.0535 (9)0.0430 (8)0.0084 (8)0.0074 (7)0.0098 (7)
C60.0488 (8)0.0478 (8)0.0353 (7)0.0145 (6)0.0011 (6)0.0094 (6)
C70.0604 (9)0.0511 (9)0.0346 (7)0.0122 (7)0.0008 (6)0.0093 (6)
C80.0506 (8)0.0450 (8)0.0334 (7)0.0081 (6)0.0000 (6)0.0049 (6)
C90.0663 (10)0.0472 (8)0.0381 (7)0.0113 (7)0.0010 (7)0.0117 (6)
C100.0667 (10)0.0371 (7)0.0470 (8)0.0084 (7)0.0042 (7)0.0098 (6)
C110.0480 (8)0.0365 (7)0.0406 (7)0.0024 (6)0.0039 (6)0.0033 (6)
C120.0411 (7)0.0389 (7)0.0347 (7)0.0050 (5)0.0027 (5)0.0065 (5)
C130.0447 (7)0.0389 (7)0.0340 (7)0.0048 (6)0.0021 (5)0.0054 (5)
C140.0553 (8)0.0374 (7)0.0352 (7)0.0057 (6)0.0006 (6)0.0032 (6)
C150.0516 (8)0.0382 (7)0.0365 (7)0.0050 (6)0.0017 (6)0.0048 (6)
C160.0812 (12)0.0400 (8)0.0578 (10)0.0107 (8)0.0073 (8)0.0002 (7)
C170.0698 (10)0.0472 (9)0.0358 (7)0.0045 (7)0.0061 (7)0.0002 (6)
C180.0644 (10)0.0424 (8)0.0387 (8)0.0060 (7)0.0004 (7)0.0074 (6)
C190.158 (2)0.0454 (10)0.0725 (13)0.0247 (12)0.0136 (13)0.0174 (9)
C200.0536 (9)0.0557 (9)0.0411 (8)0.0099 (7)0.0023 (6)0.0125 (7)
C210.0607 (10)0.0669 (11)0.0409 (8)0.0036 (8)0.0011 (7)0.0114 (7)
C220.0721 (11)0.0587 (10)0.0494 (9)0.0009 (8)0.0093 (8)0.0030 (8)
C230.0698 (11)0.0544 (10)0.0645 (11)0.0141 (8)0.0117 (9)0.0097 (8)
C240.0536 (9)0.0617 (10)0.0535 (9)0.0142 (8)0.0007 (7)0.0139 (8)
C250.0485 (8)0.0547 (9)0.0367 (7)0.0058 (7)0.0060 (6)0.0125 (6)
C260.0571 (9)0.0560 (9)0.0404 (8)0.0066 (7)0.0019 (6)0.0146 (7)
C270.0513 (8)0.0490 (8)0.0373 (7)0.0040 (6)0.0008 (6)0.0070 (6)
C280.0612 (9)0.0512 (9)0.0439 (8)0.0076 (7)0.0005 (7)0.0148 (7)
C290.0634 (10)0.0421 (8)0.0527 (9)0.0066 (7)0.0050 (7)0.0108 (7)
C300.0539 (9)0.0416 (8)0.0455 (8)0.0029 (6)0.0030 (6)0.0040 (6)
C310.0466 (8)0.0441 (8)0.0381 (7)0.0040 (6)0.0039 (6)0.0077 (6)
C320.0481 (8)0.0437 (8)0.0386 (7)0.0039 (6)0.0032 (6)0.0072 (6)
C330.0597 (9)0.0419 (8)0.0397 (7)0.0034 (7)0.0011 (6)0.0051 (6)
C340.0563 (9)0.0429 (8)0.0387 (7)0.0060 (6)0.0013 (6)0.0058 (6)
C350.0804 (12)0.0481 (9)0.0675 (11)0.0063 (8)0.0030 (9)0.0002 (8)
C360.0839 (12)0.0567 (10)0.0470 (9)0.0044 (9)0.0161 (8)0.0048 (8)
C370.0668 (10)0.0470 (9)0.0395 (8)0.0093 (7)0.0008 (7)0.0062 (6)
C380.1103 (16)0.0470 (10)0.0798 (13)0.0149 (10)0.0062 (12)0.0201 (9)
N10.0491 (7)0.0377 (6)0.0332 (6)0.0037 (5)0.0001 (5)0.0040 (5)
N20.0556 (7)0.0432 (7)0.0363 (6)0.0041 (5)0.0015 (5)0.0048 (5)
O10.0787 (7)0.0457 (6)0.0319 (5)0.0086 (5)0.0060 (5)0.0053 (4)
O20.0713 (7)0.0362 (5)0.0436 (6)0.0049 (5)0.0003 (5)0.0008 (4)
O30.1119 (10)0.0530 (7)0.0456 (6)0.0096 (7)0.0206 (6)0.0104 (5)
O40.1233 (11)0.0381 (6)0.0489 (6)0.0168 (6)0.0125 (7)0.0074 (5)
O50.0752 (7)0.0518 (6)0.0374 (5)0.0025 (5)0.0093 (5)0.0096 (5)
O60.0916 (9)0.0459 (6)0.0536 (7)0.0038 (6)0.0079 (6)0.0012 (5)
O70.1312 (12)0.0600 (8)0.0467 (7)0.0181 (8)0.0221 (7)0.0085 (6)
O80.1054 (10)0.0435 (6)0.0539 (7)0.0109 (6)0.0138 (6)0.0084 (5)
Geometric parameters (Å, º) top
C1—C21.379 (2)C20—C211.374 (2)
C1—C61.382 (2)C20—C251.388 (2)
C1—H10.9300C20—H200.9300
C2—C31.368 (3)C21—C221.375 (2)
C2—H20.9300C21—H210.9300
C3—C41.380 (3)C22—C231.380 (2)
C3—H30.9300C22—H220.9300
C4—C51.375 (2)C23—C241.379 (2)
C4—H40.9300C23—H230.9300
C5—C61.388 (2)C24—C251.384 (2)
C5—H50.9300C24—H240.9300
C6—C71.496 (2)C25—C261.495 (2)
C7—O11.4236 (16)C26—O51.4222 (17)
C7—H7A0.9700C26—H26A0.9700
C7—H7B0.9700C26—H26B0.9700
C8—C91.363 (2)C27—C281.363 (2)
C8—O11.3715 (17)C27—O51.3661 (17)
C8—C131.4129 (18)C27—C321.4144 (19)
C9—C101.408 (2)C28—C291.404 (2)
C9—H90.9300C28—H280.9300
C10—C111.371 (2)C29—C301.368 (2)
C10—H100.9300C29—H290.9300
C11—O21.3732 (16)C30—O61.3752 (18)
C11—C121.4129 (19)C30—C311.413 (2)
C12—N11.3772 (16)C31—N21.3802 (18)
C12—C131.4082 (18)C31—C321.4022 (19)
C13—C141.4139 (19)C32—C331.410 (2)
C14—C151.3672 (19)C33—C341.369 (2)
C14—H140.9300C33—H330.9300
C15—N11.3850 (17)C34—N21.3807 (18)
C15—C181.4679 (19)C34—C371.468 (2)
C16—O21.4196 (18)C35—O61.409 (2)
C16—H16A0.9600C35—H35A0.9600
C16—H16B0.9600C35—H35B0.9600
C16—H16C0.9600C35—H35C0.9600
C17—N11.4551 (17)C36—N21.4591 (19)
C17—H17A0.9600C36—H36A0.9600
C17—H17B0.9600C36—H36B0.9600
C17—H17C0.9600C36—H36C0.9600
C18—O31.2005 (18)C37—O71.1986 (18)
C18—O41.3325 (18)C37—O81.3287 (18)
C19—O41.441 (2)C38—O81.446 (2)
C19—H19A0.9600C38—H38A0.9600
C19—H19B0.9600C38—H38B0.9600
C19—H19C0.9600C38—H38C0.9600
C2—C1—C6120.56 (16)C21—C22—C23119.26 (16)
C2—C1—H1119.7C21—C22—H22120.4
C6—C1—H1119.7C23—C22—H22120.4
C3—C2—C1120.31 (16)C24—C23—C22120.38 (16)
C3—C2—H2119.8C24—C23—H23119.8
C1—C2—H2119.8C22—C23—H23119.8
C2—C3—C4119.77 (17)C23—C24—C25120.72 (15)
C2—C3—H3120.1C23—C24—H24119.6
C4—C3—H3120.1C25—C24—H24119.6
C5—C4—C3120.18 (17)C24—C25—C20118.19 (14)
C5—C4—H4119.9C24—C25—C26122.53 (13)
C3—C4—H4119.9C20—C25—C26119.24 (14)
C4—C5—C6120.49 (15)O5—C26—C25109.67 (12)
C4—C5—H5119.8O5—C26—H26A109.7
C6—C5—H5119.8C25—C26—H26A109.7
C1—C6—C5118.69 (14)O5—C26—H26B109.7
C1—C6—C7119.86 (14)C25—C26—H26B109.7
C5—C6—C7121.42 (13)H26A—C26—H26B108.2
O1—C7—C6108.96 (12)C28—C27—O5126.64 (13)
O1—C7—H7A109.9C28—C27—C32118.10 (13)
C6—C7—H7A109.9O5—C27—C32115.26 (13)
O1—C7—H7B109.9C27—C28—C29120.96 (14)
C6—C7—H7B109.9C27—C28—H28119.5
H7A—C7—H7B108.3C29—C28—H28119.5
C9—C8—O1126.36 (13)C30—C29—C28122.72 (14)
C9—C8—C13118.56 (13)C30—C29—H29118.6
O1—C8—C13115.09 (12)C28—C29—H29118.6
C8—C9—C10120.92 (13)C29—C30—O6125.43 (14)
C8—C9—H9119.5C29—C30—C31116.82 (13)
C10—C9—H9119.5O6—C30—C31117.75 (13)
C11—C10—C9122.34 (13)N2—C31—C32108.04 (12)
C11—C10—H10118.8N2—C31—C30130.95 (13)
C9—C10—H10118.8C32—C31—C30121.00 (13)
C10—C11—O2124.41 (13)C31—C32—C33107.24 (12)
C10—C11—C12117.17 (13)C31—C32—C27120.38 (13)
O2—C11—C12118.42 (12)C33—C32—C27132.35 (13)
N1—C12—C13107.93 (11)C34—C33—C32107.24 (13)
N1—C12—C11131.19 (12)C34—C33—H33126.4
C13—C12—C11120.88 (12)C32—C33—H33126.4
C12—C13—C8120.06 (12)C33—C34—N2109.64 (12)
C12—C13—C14107.30 (11)C33—C34—C37127.48 (14)
C8—C13—C14132.60 (13)N2—C34—C37122.87 (13)
C15—C14—C13107.01 (12)O6—C35—H35A109.5
C15—C14—H14126.5O6—C35—H35B109.5
C13—C14—H14126.5H35A—C35—H35B109.5
C14—C15—N1109.88 (12)O6—C35—H35C109.5
C14—C15—C18127.42 (13)H35A—C35—H35C109.5
N1—C15—C18122.69 (12)H35B—C35—H35C109.5
O2—C16—H16A109.5N2—C36—H36A109.5
O2—C16—H16B109.5N2—C36—H36B109.5
H16A—C16—H16B109.5H36A—C36—H36B109.5
O2—C16—H16C109.5N2—C36—H36C109.5
H16A—C16—H16C109.5H36A—C36—H36C109.5
H16B—C16—H16C109.5H36B—C36—H36C109.5
N1—C17—H17A109.5O7—C37—O8122.61 (14)
N1—C17—H17B109.5O7—C37—C34126.56 (15)
H17A—C17—H17B109.5O8—C37—C34110.83 (13)
N1—C17—H17C109.5O8—C38—H38A109.5
H17A—C17—H17C109.5O8—C38—H38B109.5
H17B—C17—H17C109.5H38A—C38—H38B109.5
O3—C18—O4122.79 (14)O8—C38—H38C109.5
O3—C18—C15126.74 (14)H38A—C38—H38C109.5
O4—C18—C15110.46 (12)H38B—C38—H38C109.5
O4—C19—H19A109.5C12—N1—C15107.88 (11)
O4—C19—H19B109.5C12—N1—C17125.66 (12)
H19A—C19—H19B109.5C15—N1—C17126.24 (11)
O4—C19—H19C109.5C31—N2—C34107.83 (11)
H19A—C19—H19C109.5C31—N2—C36125.27 (13)
H19B—C19—H19C109.5C34—N2—C36126.61 (13)
C21—C20—C25121.04 (15)C8—O1—C7116.60 (11)
C21—C20—H20119.5C11—O2—C16116.44 (11)
C25—C20—H20119.5C18—O4—C19116.04 (13)
C20—C21—C22120.38 (15)C27—O5—C26116.35 (12)
C20—C21—H21119.8C30—O6—C35117.35 (13)
C22—C21—H21119.8C37—O8—C38117.08 (13)
C6—C1—C2—C30.7 (3)C29—C30—C31—N2177.77 (15)
C1—C2—C3—C40.1 (3)O6—C30—C31—N21.7 (2)
C2—C3—C4—C50.5 (3)C29—C30—C31—C321.1 (2)
C3—C4—C5—C60.5 (3)O6—C30—C31—C32179.44 (13)
C2—C1—C6—C50.6 (2)N2—C31—C32—C330.50 (16)
C2—C1—C6—C7177.57 (14)C30—C31—C32—C33179.63 (14)
C4—C5—C6—C10.0 (2)N2—C31—C32—C27177.89 (13)
C4—C5—C6—C7178.14 (14)C30—C31—C32—C271.2 (2)
C1—C6—C7—O1142.32 (14)C28—C27—C32—C310.4 (2)
C5—C6—C7—O139.53 (19)O5—C27—C32—C31179.26 (13)
O1—C8—C9—C10178.78 (14)C28—C27—C32—C33178.38 (16)
C13—C8—C9—C101.1 (2)O5—C27—C32—C331.3 (2)
C8—C9—C10—C111.4 (2)C31—C32—C33—C340.52 (17)
C9—C10—C11—O2179.80 (14)C27—C32—C33—C34177.60 (16)
C9—C10—C11—C120.6 (2)C32—C33—C34—N20.35 (18)
C10—C11—C12—N1178.50 (14)C32—C33—C34—C37179.86 (15)
O2—C11—C12—N10.8 (2)C33—C34—C37—O7177.51 (18)
C10—C11—C12—C132.9 (2)N2—C34—C37—O71.9 (3)
O2—C11—C12—C13177.83 (12)C33—C34—C37—O82.2 (2)
N1—C12—C13—C8177.81 (13)N2—C34—C37—O8178.31 (14)
C11—C12—C13—C83.3 (2)C13—C12—N1—C150.05 (15)
N1—C12—C13—C140.37 (15)C11—C12—N1—C15178.80 (14)
C11—C12—C13—C14178.54 (13)C13—C12—N1—C17174.95 (13)
C9—C8—C13—C121.2 (2)C11—C12—N1—C176.3 (2)
O1—C8—C13—C12178.89 (12)C14—C15—N1—C120.47 (16)
C9—C8—C13—C14178.88 (15)C18—C15—N1—C12178.30 (14)
O1—C8—C13—C141.3 (2)C14—C15—N1—C17175.33 (14)
C12—C13—C14—C150.64 (16)C18—C15—N1—C173.4 (2)
C8—C13—C14—C15177.22 (16)C32—C31—N2—C340.29 (16)
C13—C14—C15—N10.69 (17)C30—C31—N2—C34179.30 (15)
C13—C14—C15—C18178.00 (15)C32—C31—N2—C36173.88 (14)
C14—C15—C18—O3177.52 (17)C30—C31—N2—C365.1 (3)
N1—C15—C18—O31.0 (3)C33—C34—N2—C310.04 (17)
C14—C15—C18—O42.1 (2)C37—C34—N2—C31179.58 (14)
N1—C15—C18—O4179.32 (13)C33—C34—N2—C36174.12 (15)
C25—C20—C21—C221.1 (2)C37—C34—N2—C366.3 (2)
C20—C21—C22—C230.0 (3)C9—C8—O1—C711.2 (2)
C21—C22—C23—C241.0 (3)C13—C8—O1—C7168.92 (13)
C22—C23—C24—C250.9 (3)C6—C7—O1—C8178.88 (12)
C23—C24—C25—C200.2 (2)C10—C11—O2—C1611.5 (2)
C23—C24—C25—C26177.36 (15)C12—C11—O2—C16169.30 (13)
C21—C20—C25—C241.2 (2)O3—C18—O4—C192.4 (3)
C21—C20—C25—C26176.43 (14)C15—C18—O4—C19177.29 (18)
C24—C25—C26—O534.3 (2)C28—C27—O5—C267.6 (2)
C20—C25—C26—O5148.11 (14)C32—C27—O5—C26172.04 (13)
O5—C27—C28—C29179.94 (14)C25—C26—O5—C27175.97 (12)
C32—C27—C28—C290.4 (2)C29—C30—O6—C352.4 (2)
C27—C28—C29—C300.5 (3)C31—C30—O6—C35178.20 (15)
C28—C29—C30—O6179.67 (15)O7—C37—O8—C380.8 (3)
C28—C29—C30—C310.3 (2)C34—C37—O8—C38178.94 (17)
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C20–C25 phenyl ring, C1–C6 phenyl ring, C27–C32 phenyl ring and C12–C15/N1 pyrrole ring, respectively.
D—H···AD—HH···AD···AD—H···A
C5—H5···Cg10.932.883.6778 (7)145
C16—H16A···Cg2i0.962.873.7812 (9)158
C17—H17C···Cg3ii0.962.903.845 (1)167
C26—H26A···Cg4iii0.962.943.7442 (8)141
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC19H19NO4
Mr325.35
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.622 (2), 12.871 (4), 16.928 (5)
α, β, γ (°)93.831 (3), 100.158 (3), 93.456 (3)
V3)1626.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.38 × 0.36 × 0.25
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.965, 0.977
No. of measured, independent and
observed [I > 2σ(I)] reflections
19234, 7421, 5286
Rint0.023
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.134, 1.05
No. of reflections7421
No. of parameters440
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.17

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C20–C25 phenyl ring, C1–C6 phenyl ring, C27–C32 phenyl ring and C12–C15/N1 pyrrole ring, respectively.
D—H···AD—HH···AD···AD—H···A
C5—H5···Cg10.93002.8763.6778 (7)145.1
C16—H16A···Cg2i0.96002.8733.7812 (9)158.2
C17—H17C···Cg3ii0.96002.9043.845 (1)166.8
C26—H26A···Cg4iii0.96002.9443.7442 (8)140.6
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x+1, y, z.
 

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21072115) and Shandong Natural Science Foundation (grant No. ZR2011HM042).

References

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First citationBruker (2005). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.   Google Scholar
First citationButcher, R. J., Jasinski, J. P., Yathirajan, H. S., Ashalatha, B. V. & Narayana, B. (2007). Acta Cryst. E63, o3505.  Web of Science CSD CrossRef IUCr Journals Google Scholar
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First citationHu, S.-C., Tan, R.-X., Hong, K., Yu, Z.-N. & Zhu, H.-L. (2005). Acta Cryst. E61, o1654–o1656.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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