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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

(3,5-Di­methyl-1H-pyrazol-1-yl){3-[(3,5-di­methyl-1H-pyrazol-1-yl)carbon­yl]-5-methyl­indolizin-1-yl}methanone

aDepartment of Applied Chemistry, Nanjing Normal University, Nanjing 210097, People's Republic of China, bKey Laboratory of Applied Photochemistry, Nanjing Normal University, Nanjing 210097, People's Republic of China, and cJiangsu Key Laboratory of Biofunctional Materials, Jiangsu Research Center of Biomedical Functional Materials Engineering, Nanjing Normal University, Nanjing 210097, People's Republic of China
*Correspondence e-mail: wangnjnuchem@163.com

(Received 28 January 2013; accepted 21 February 2013; online 28 February 2013)

There are two independent mol­ecules in the asymmetric unit of the title compound, C21H21N5O2. In each mol­ecule, the indolizine ring system is essentially planar, with r.m.s. deviations of 0.030 and 0.028 Å. The dihedral angles between the indolizine ring system and the pyrazole rings are 54.7 (3) and 8.6 (3)° in one mol­ecule and 54.4 (3) and 6.6 (3)° in the other. In the crystal, weak C—H⋯O and C—H⋯N hydrogen bonds link mol­ecules, forming a two-dimensional network parallel to (100).

Related literature

For the biological applications of indolizines and pyrazoles, see: Tukulula et al. (2010[Tukulula, M., Klein, R. & Kaye, P. T. (2010). Synth. Commun. 40, 2018-2028.]); James et al. (2008[James, D. A., Koya, K., Li, H., Liang, G. Q., Xia, Z. Q., Ying, W. W., Wu, Y. M. & Sun, L. J. (2008). Bioorg. Med. Chem. Lett. 18, 1784-1787.]); Teklu et al. (2005[Teklu, S., Gundersen, L. L., Larsen, T., Malterud, K. E. & Rise, F. (2005). Bioorg. Med. Chem. 13, 3127-3139.]); McDonald et al. (2006[McDonald, E., Workman, P. & Jones, K. (2006). Curr. Top. Med. Chem. 6, 1091-1107.]); Jagerovic et al. (2002[Jagerovic, N., Cano, C., Elguero, J. & Goya, P. (2002). Bioorg. Med. Chem. 10, 817-827.]). For background to and the synthesis of related hetrocycles, see: Gu et al. (2011[Gu, W.-J., Zhuang, J., Jiang, Y.-L. & Wang, B.-X. (2011). Acta Cryst. E67, o123.]); Shen et al. (2006[Shen, Y.-M., Wang, B.-X., Feng, Y.-Y., Shen, Z.-Y., Shen, J., Li, C. & Hu, H.-W. (2006). Chem. J. Chin. Univ. Chin. 27, 651-653.], 2008[Shen, Z.-Y., Wang, B.-X., Shen, J. & Hu, H.-W. (2008). Chem. J. Chin. Univ. Chin. 29, 916-918.]); Wang, et al. (2000[Wang, B.-X., Hu, J.-X., Zhang, X.-C., Hu, Y.-F. & Hu, H.-W. (2000). J. Heterocycl Chem. 37, 1533-1537. ]).

[Scheme 1]

Experimental

Crystal data
  • C21H21N5O2

  • Mr = 375.43

  • Orthorhombic, P c a 21

  • a = 19.7286 (11) Å

  • b = 11.5659 (14) Å

  • c = 17.8088 (18) Å

  • V = 4063.6 (7) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 291 K

  • 0.26 × 0.22 × 0.20 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.979, Tmax = 0.984

  • 30693 measured reflections

  • 7955 independent reflections

  • 6221 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.129

  • S = 1.07

  • 7955 reflections

  • 516 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C12—H12⋯O2i 0.93 2.37 3.282 (4) 167
C21—H21B⋯O1ii 0.96 2.59 3.404 (4) 142
C30—H30C⋯N3iii 0.96 2.52 3.472 (4) 169
C33—H33⋯O4iv 0.93 2.55 3.393 (4) 152
Symmetry codes: (i) x, y-1, z; (ii) [-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]; (iii) [x-{\script{1\over 2}}, -y+1, z]; (iv) x, y+1, z.

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Indolizines and pyrazoles are important classes of bio-active drug targets in the pharmaceutical industry, as they are the core structure of numerous biologically active compounds (Tukulula et al., 2010; James et al., 2008; Teklu et al., 2005; McDonald et al., 2006; Jagerovic et al., 2002). In our continuing studies on the synthesis and properties of heterocycles (Gu et al., 2011; Shen et al., 2008; Shen et al., 2006; Wang, et al., 2000) we have prepared (Fig. 1) and determined the crystal structure of the title compound .

The molecular structure of the title compound is shown in Fig. 2. There are two independent molecules is the asymmetric unit. The r.m.s deviation for the indolizine rings systems N1/C1-C8 and N6/C22-C29 are 0.030 and 0.028 Å, respectively. The dihedral angle between N1/C1-C8 and N2/N3/C11-C13 is 125.3 (3) °, N1/C1-C8 and N4/N5/C17-C19 is 8.6 (3)°, N6/C22-C29 and N7/N8/C32-C34 is 125.6 (3)°, and N6/C22-C29 and N9/N10/C38-C40 = 6.6 (3)°. In the crystal weak C—H···O and C—H···N hydrogen bonds link molecules to form a two-dimensional network parallel to (100).

Related literature top

For the biological applications of indolizines and pyrazoles, see: Tukulula et al. (2010); James et al. (2008); Teklu et al. (2005); McDonald et al. (2006); Jagerovic et al. (2002). For background to and the synthesis of related hetrocycles, see: Gu et al. (2011); Shen et al. (2006, 2008); Wang, et al. (2000).

Experimental top

3-ethyl 1-methyl 5-methylindolizine-1,3-dicarboxylate was prepared through 1,3-dipolar cycloaddition according to a procedure described in the literature (Wang, et al., 2000). A suspension of N-(carbethoxymethyl)-2-ethylpyridinium bromide (C6H7N+CH2COOC2H5.Br-) (10 mmol), methyl acrylate (40 mmol), Et3N (60 ml) and CrO3 (80 mmol) in DMF (40 ml) was stirred at 363K for 4 h (monitored by TLC). The mixture was cooled to room temperature and poured into 5% aqueous HCl (150 mL). The deep brown power was collected by filtration and washed with ethanol (20 mL) After drying the solid was collected 1.32 g (51%).

3-ethyl 1-methyl 5-methylindolizine-1,3-dicarboxylate (5 mmol) was dissolved in 6 ml of ethanol and 30 ml 80% N2H4.H2O (45 mmol) was added dropwise. The solution was refluxed for 8 h and cooled to yield the product, 0.69 g (56%) as 5-methylindolizine-1,3-dicarbohydrazide.

5-methylindolizine-1,3-dicarbohydrazide (1 mmol) was dissolved in 2 ml acetic acid, then acetylacetone (4 mmol, dissolved in 4ml ethanol) was added. After stirring for 4 h, the mixture was purified by chromatography [silica gel, 20% ethyl acetate in petroleum ether (60 C90)] to yield colorless block crystals of the title compound, 0.26 g (70%). 1H-NMR (CDCl3, 400 MHz): 2.27 (s, 3H, –CH3), 2.31 (s, 3H, –CH3), 2.63 (s, 3H, –CH3), 2.64 (s, 6H, –CH3, –CH3), 6.02 (s, 1H, pyrazole =CH), 6.10(s, 1H, pyrazole =CH), 6.94 (d, 1H, indolizine =CH), 7.45 (t, 1H, indolizine =CH), 8.52 (s, 1H, indolizine =CH), 8.55 (d, 1H, indolizine =CH).

Refinement top

H atoms were placed in calculated positions with C—H = 0.93 and 0.96Å. They were included in a riding-motion approximation with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(Cmethyl).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The reaction scheme.
[Figure 2] Fig. 2. The asymmetric unit of title compound. Displacement ellipsoids at the 50% probability level.
(3,5-Dimethyl-1H-pyrazol-1-yl){3-[(3,5-dimethyl-1H-pyrazol-1-yl)carbonyl]-5-methylindolizin-1-yl}methanone top
Crystal data top
C21H21N5O2F(000) = 1584
Mr = 375.43Dx = 1.227 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 5647 reflections
a = 19.7286 (11) Åθ = 2.3–21.7°
b = 11.5659 (14) ŵ = 0.08 mm1
c = 17.8088 (18) ÅT = 291 K
V = 4063.6 (7) Å3Block, colourless
Z = 80.26 × 0.22 × 0.20 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
7955 independent reflections
Radiation source: sealed tube6221 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 2423
Tmin = 0.979, Tmax = 0.984k = 1214
30693 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.05P)2 + 1.55P]
where P = (Fo2 + 2Fc2)/3
7955 reflections(Δ/σ)max < 0.001
516 parametersΔρmax = 0.19 e Å3
1 restraintΔρmin = 0.25 e Å3
Crystal data top
C21H21N5O2V = 4063.6 (7) Å3
Mr = 375.43Z = 8
Orthorhombic, Pca21Mo Kα radiation
a = 19.7286 (11) ŵ = 0.08 mm1
b = 11.5659 (14) ÅT = 291 K
c = 17.8088 (18) Å0.26 × 0.22 × 0.20 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
7955 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
6221 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.984Rint = 0.025
30693 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0501 restraint
wR(F2) = 0.129H-atom parameters constrained
S = 1.07Δρmax = 0.19 e Å3
7955 reflectionsΔρmin = 0.25 e Å3
516 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
C10.95788 (15)0.4268 (3)0.79194 (16)0.0511 (7)
C20.97669 (16)0.5313 (3)0.81916 (17)0.0537 (8)
H21.01130.53450.85450.064*
C30.94637 (15)0.6336 (3)0.79647 (17)0.0504 (7)
H30.95990.70360.81740.061*
C40.89665 (16)0.6313 (3)0.74333 (17)0.0517 (7)
H40.87860.70030.72540.062*
C50.87266 (15)0.5260 (3)0.71560 (16)0.0470 (7)
C60.82339 (15)0.4954 (3)0.66095 (15)0.0471 (7)
C70.82505 (15)0.3748 (3)0.65706 (16)0.0502 (7)
H70.79840.33070.62490.060*
C80.87156 (15)0.3292 (3)0.70735 (17)0.0479 (7)
C90.99612 (15)0.3185 (2)0.80885 (16)0.0487 (7)
H9A0.97040.27170.84310.073*
H9B1.03890.33780.83120.073*
H9C1.00370.27630.76320.073*
C100.86911 (16)0.2129 (3)0.73751 (17)0.0506 (7)
C110.83518 (16)0.0113 (3)0.70175 (17)0.0524 (7)
C120.82865 (17)0.0416 (3)0.63537 (17)0.0544 (8)
H120.81440.11730.62780.065*
C130.84745 (16)0.0390 (3)0.57820 (18)0.0542 (8)
C140.82015 (17)0.0311 (3)0.77875 (18)0.0588 (8)
H14A0.79980.10640.77580.088*
H14B0.78950.02130.80310.088*
H14C0.86150.03580.80700.088*
C150.85063 (17)0.0238 (3)0.49569 (17)0.0569 (8)
H15A0.87060.09120.47330.085*
H15B0.80570.01320.47630.085*
H15C0.87770.04280.48400.085*
C160.78392 (15)0.5808 (3)0.62317 (16)0.0483 (7)
C170.69986 (16)0.6164 (3)0.51854 (18)0.0532 (7)
C180.66236 (15)0.5437 (3)0.47619 (16)0.0489 (7)
H180.63260.56460.43810.059*
C190.67648 (15)0.4313 (3)0.50014 (18)0.0533 (7)
C200.70343 (15)0.7452 (2)0.51772 (18)0.0523 (8)
H20A0.67590.77450.47760.078*
H20B0.74960.76900.51040.078*
H20C0.68710.77490.56470.078*
C210.64842 (16)0.3191 (3)0.47238 (17)0.0546 (7)
H21A0.67080.25630.49740.082*
H21B0.65580.31310.41920.082*
H21C0.60070.31590.48270.082*
C220.41826 (16)0.5455 (3)0.49679 (16)0.0493 (7)
C230.39368 (16)0.4389 (3)0.48031 (17)0.0527 (8)
H230.35750.43250.44710.063*
C240.42111 (17)0.3377 (3)0.51186 (18)0.0545 (8)
H240.40410.26580.49800.065*
C250.47187 (16)0.3449 (3)0.56205 (18)0.0537 (7)
H250.48830.27830.58490.064*
C260.50012 (16)0.4536 (3)0.57998 (17)0.0511 (7)
C270.55051 (15)0.4910 (3)0.63101 (16)0.0474 (7)
C280.55515 (15)0.6100 (3)0.62361 (16)0.0478 (7)
H280.58460.65700.65070.057*
C290.51025 (14)0.6481 (3)0.57084 (17)0.0480 (7)
C300.38317 (16)0.6508 (3)0.47244 (16)0.0529 (7)
H30A0.34020.63060.45090.079*
H30B0.41020.69020.43560.079*
H30C0.37620.70060.51490.079*
C310.51566 (15)0.7556 (3)0.52786 (17)0.0503 (7)
C320.55300 (16)0.9622 (3)0.54312 (16)0.0525 (7)
C330.55914 (16)1.0296 (3)0.60368 (18)0.0557 (8)
H330.57251.10670.60420.067*
C340.54178 (16)0.9629 (3)0.66563 (18)0.0544 (8)
C350.56546 (17)0.9886 (3)0.46158 (17)0.0570 (8)
H35A0.58481.06440.45700.086*
H35B0.52330.98560.43470.086*
H35C0.59620.93250.44110.086*
C360.53860 (17)0.9990 (3)0.74706 (17)0.0555 (8)
H36A0.58341.01640.76470.083*
H36B0.51990.93720.77640.083*
H36C0.51051.06630.75180.083*
C370.58944 (16)0.4080 (3)0.67483 (17)0.0502 (7)
C380.68154 (15)0.3805 (3)0.77224 (18)0.0501 (7)
C390.71764 (15)0.4592 (3)0.81277 (17)0.0488 (7)
H390.75070.44250.84840.059*
C400.69609 (16)0.5699 (3)0.79131 (17)0.0504 (7)
C410.68581 (16)0.2528 (2)0.77334 (18)0.0551 (8)
H41A0.64420.22140.79250.083*
H41B0.72270.22930.80500.083*
H41C0.69320.22470.72330.083*
C420.71876 (17)0.6851 (3)0.81811 (18)0.0525 (7)
H42A0.68450.71790.84990.079*
H42B0.72620.73500.77580.079*
H42C0.76020.67690.84590.079*
N10.90253 (12)0.4237 (2)0.74381 (13)0.0477 (6)
N20.85490 (14)0.1237 (2)0.68550 (15)0.0589 (7)
N30.86355 (13)0.1389 (2)0.60984 (14)0.0518 (6)
N40.73572 (13)0.5457 (2)0.56655 (14)0.0507 (6)
N50.72100 (12)0.4309 (2)0.55560 (13)0.0478 (6)
N60.47486 (12)0.5511 (2)0.54330 (13)0.0465 (6)
N70.53127 (12)0.8556 (2)0.56983 (14)0.0497 (6)
N80.52484 (13)0.8577 (2)0.64599 (14)0.0520 (6)
N90.63732 (13)0.4465 (2)0.72789 (14)0.0481 (6)
N100.64724 (13)0.5633 (2)0.74015 (14)0.0515 (6)
O10.87568 (11)0.18868 (18)0.80311 (12)0.0559 (5)
O20.78751 (10)0.68345 (17)0.63626 (12)0.0531 (5)
O30.51202 (11)0.76188 (18)0.46034 (12)0.0556 (5)
O40.58222 (10)0.30270 (18)0.66841 (12)0.0559 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0487 (16)0.0568 (19)0.0479 (17)0.0042 (14)0.0005 (13)0.0006 (14)
C20.0537 (18)0.060 (2)0.0475 (16)0.0095 (16)0.0077 (14)0.0062 (15)
C30.0493 (17)0.0514 (18)0.0507 (17)0.0049 (13)0.0012 (14)0.0048 (14)
C40.0563 (17)0.0508 (18)0.0479 (16)0.0081 (14)0.0041 (14)0.0021 (14)
C50.0477 (16)0.0447 (17)0.0487 (16)0.0059 (13)0.0069 (13)0.0018 (13)
C60.0491 (16)0.0463 (16)0.0458 (16)0.0060 (13)0.0026 (13)0.0044 (13)
C70.0487 (17)0.0537 (18)0.0483 (17)0.0001 (14)0.0011 (14)0.0025 (14)
C80.0518 (17)0.0440 (17)0.0481 (16)0.0029 (13)0.0025 (13)0.0031 (13)
C90.0539 (17)0.0483 (17)0.0437 (15)0.0058 (13)0.0063 (14)0.0008 (13)
C100.0561 (17)0.0475 (17)0.0483 (17)0.0033 (13)0.0022 (14)0.0007 (14)
C110.0575 (18)0.0504 (18)0.0494 (17)0.0066 (14)0.0094 (14)0.0073 (14)
C120.067 (2)0.0446 (17)0.0517 (17)0.0039 (14)0.0111 (15)0.0017 (14)
C130.0612 (19)0.0468 (17)0.0547 (18)0.0058 (15)0.0136 (15)0.0012 (14)
C140.0580 (18)0.0523 (18)0.066 (2)0.0113 (15)0.0160 (16)0.0099 (16)
C150.0592 (18)0.0564 (19)0.0552 (18)0.0045 (15)0.0096 (15)0.0069 (15)
C160.0484 (17)0.0477 (18)0.0488 (17)0.0028 (13)0.0020 (13)0.0016 (14)
C170.0559 (18)0.0517 (18)0.0520 (17)0.0022 (15)0.0046 (15)0.0007 (14)
C180.0502 (17)0.0511 (18)0.0453 (16)0.0023 (13)0.0048 (13)0.0042 (13)
C190.0468 (16)0.058 (2)0.0550 (18)0.0021 (14)0.0013 (15)0.0055 (15)
C200.0523 (17)0.0487 (17)0.0559 (18)0.0135 (14)0.0115 (14)0.0164 (14)
C210.0525 (17)0.0573 (19)0.0539 (17)0.0059 (15)0.0098 (14)0.0044 (15)
C220.0558 (17)0.0493 (18)0.0427 (15)0.0023 (14)0.0064 (14)0.0066 (13)
C230.0522 (17)0.0539 (19)0.0519 (18)0.0085 (15)0.0076 (14)0.0168 (15)
C240.0609 (18)0.0454 (18)0.0572 (18)0.0133 (14)0.0017 (15)0.0182 (14)
C250.0562 (18)0.0499 (17)0.0552 (18)0.0071 (14)0.0003 (15)0.0079 (14)
C260.0520 (17)0.0531 (19)0.0482 (16)0.0041 (14)0.0097 (14)0.0098 (14)
C270.0509 (17)0.0446 (16)0.0468 (16)0.0083 (13)0.0058 (13)0.0074 (13)
C280.0493 (16)0.0452 (17)0.0489 (16)0.0076 (13)0.0021 (13)0.0002 (13)
C290.0463 (16)0.0491 (17)0.0486 (16)0.0036 (13)0.0083 (13)0.0023 (13)
C300.0591 (18)0.0541 (18)0.0454 (16)0.0058 (15)0.0070 (14)0.0125 (14)
C310.0545 (17)0.0499 (18)0.0466 (18)0.0005 (14)0.0022 (14)0.0026 (13)
C320.0569 (18)0.0515 (19)0.0492 (17)0.0020 (14)0.0061 (14)0.0090 (14)
C330.0571 (18)0.0487 (17)0.0613 (19)0.0173 (14)0.0033 (16)0.0021 (15)
C340.0593 (19)0.0457 (18)0.0582 (18)0.0158 (14)0.0006 (15)0.0120 (14)
C350.066 (2)0.0476 (18)0.0575 (18)0.0112 (15)0.0214 (16)0.0127 (15)
C360.0614 (19)0.0504 (18)0.0549 (17)0.0115 (15)0.0045 (15)0.0142 (14)
C370.0562 (18)0.0437 (18)0.0507 (17)0.0041 (14)0.0051 (14)0.0004 (14)
C380.0477 (16)0.0441 (17)0.0584 (17)0.0027 (14)0.0088 (14)0.0083 (14)
C390.0497 (16)0.0548 (18)0.0419 (15)0.0073 (14)0.0035 (13)0.0146 (14)
C400.0499 (16)0.0487 (18)0.0525 (18)0.0090 (13)0.0038 (14)0.0005 (14)
C410.0500 (16)0.0517 (18)0.0637 (19)0.0089 (14)0.0074 (14)0.0190 (16)
C420.0588 (18)0.0482 (17)0.0506 (17)0.0168 (14)0.0049 (14)0.0025 (14)
N10.0485 (14)0.0555 (15)0.0391 (12)0.0067 (11)0.0028 (11)0.0020 (11)
N20.0690 (18)0.0496 (16)0.0581 (17)0.0013 (13)0.0064 (13)0.0029 (13)
N30.0610 (16)0.0441 (14)0.0503 (14)0.0074 (11)0.0173 (12)0.0014 (11)
N40.0544 (15)0.0466 (15)0.0512 (14)0.0010 (11)0.0023 (12)0.0004 (11)
N50.0492 (14)0.0463 (14)0.0479 (14)0.0052 (11)0.0036 (11)0.0062 (11)
N60.0497 (14)0.0427 (14)0.0472 (14)0.0042 (11)0.0043 (11)0.0100 (11)
N70.0535 (14)0.0441 (14)0.0517 (14)0.0040 (11)0.0011 (12)0.0037 (11)
N80.0593 (15)0.0440 (14)0.0527 (15)0.0081 (12)0.0017 (12)0.0063 (11)
N90.0506 (13)0.0431 (14)0.0505 (14)0.0012 (11)0.0022 (11)0.0038 (11)
N100.0580 (16)0.0457 (15)0.0506 (14)0.0040 (12)0.0046 (12)0.0042 (11)
O10.0595 (13)0.0548 (12)0.0535 (13)0.0116 (10)0.0011 (10)0.0043 (10)
O20.0549 (12)0.0458 (13)0.0587 (12)0.0054 (9)0.0090 (10)0.0019 (10)
O30.0619 (13)0.0538 (13)0.0512 (13)0.0047 (10)0.0072 (10)0.0049 (10)
O40.0599 (13)0.0477 (13)0.0602 (13)0.0003 (10)0.0137 (11)0.0006 (10)
Geometric parameters (Å, º) top
C1—C21.354 (4)C22—C301.467 (4)
C1—N11.389 (4)C23—C241.406 (4)
C1—C91.493 (4)C23—H230.9300
C2—C31.387 (4)C24—C251.345 (4)
C2—H20.9300C24—H240.9300
C3—C41.363 (4)C25—C261.412 (4)
C3—H30.9300C25—H250.9300
C4—C51.397 (4)C26—N61.395 (4)
C4—H40.9300C26—C271.415 (4)
C5—N11.414 (4)C27—C281.386 (4)
C5—C61.420 (4)C27—C371.456 (4)
C6—C71.397 (4)C28—C291.365 (4)
C6—C161.427 (4)C28—H280.9300
C7—C81.387 (4)C29—N61.410 (4)
C7—H70.9300C29—C311.463 (4)
C8—N11.411 (4)C30—H30A0.9600
C8—C101.448 (4)C30—H30B0.9600
C9—H9A0.9600C30—H30C0.9600
C9—H9B0.9600C31—O31.207 (3)
C9—H9C0.9600C31—N71.411 (4)
C10—O11.209 (3)C32—C331.337 (4)
C10—N21.415 (4)C32—N71.389 (4)
C11—C121.337 (4)C32—C351.504 (4)
C11—N21.387 (4)C33—C341.389 (4)
C11—C141.486 (4)C33—H330.9300
C12—C131.429 (4)C34—N81.310 (4)
C12—H120.9300C34—C361.510 (4)
C13—N31.324 (4)C35—H35A0.9600
C13—C151.481 (4)C35—H35B0.9600
C14—H14A0.9600C35—H35C0.9600
C14—H14B0.9600C36—H36A0.9600
C14—H14C0.9600C36—H36B0.9600
C15—H15A0.9600C36—H36C0.9600
C15—H15B0.9600C37—O41.231 (3)
C15—H15C0.9600C37—N91.408 (4)
C16—O21.212 (3)C38—C391.363 (4)
C16—N41.444 (4)C38—N91.403 (4)
C17—C181.350 (4)C38—C411.480 (4)
C17—N41.379 (4)C39—C401.402 (4)
C17—C201.491 (4)C39—H390.9300
C18—C191.395 (4)C40—N101.328 (4)
C18—H180.9300C40—C421.484 (4)
C19—N51.322 (4)C41—H41A0.9600
C19—C211.495 (4)C41—H41B0.9600
C20—H20A0.9600C41—H41C0.9600
C20—H20B0.9600C42—H42A0.9600
C20—H20C0.9600C42—H42B0.9600
C21—H21A0.9600C42—H42C0.9600
C21—H21B0.9600N2—N31.370 (4)
C21—H21C0.9600N4—N51.373 (3)
C22—C231.357 (4)N7—N81.362 (3)
C22—N61.392 (4)N9—N101.382 (3)
C2—C1—N1117.3 (3)C26—C25—H25120.0
C2—C1—C9122.6 (3)N6—C26—C25118.2 (3)
N1—C1—C9120.0 (3)N6—C26—C27107.7 (3)
C1—C2—C3122.6 (3)C25—C26—C27134.0 (3)
C1—C2—H2118.7C28—C27—C26106.8 (3)
C3—C2—H2118.7C28—C27—C37132.2 (3)
C4—C3—C2119.7 (3)C26—C27—C37120.9 (3)
C4—C3—H3120.1C29—C28—C27110.1 (3)
C2—C3—H3120.1C29—C28—H28125.0
C3—C4—C5120.4 (3)C27—C28—H28125.0
C3—C4—H4119.8C28—C29—N6107.7 (3)
C5—C4—H4119.8C28—C29—C31126.0 (3)
C4—C5—N1117.6 (3)N6—C29—C31122.0 (3)
C4—C5—C6133.7 (3)C22—C30—H30A109.5
N1—C5—C6108.7 (3)C22—C30—H30B109.5
C7—C6—C5105.5 (2)H30A—C30—H30B109.5
C7—C6—C16132.9 (3)C22—C30—H30C109.5
C5—C6—C16121.6 (3)H30A—C30—H30C109.5
C8—C7—C6111.3 (3)H30B—C30—H30C109.5
C8—C7—H7124.3O3—C31—N7119.4 (3)
C6—C7—H7124.3O3—C31—C29124.6 (3)
C7—C8—N1106.8 (3)N7—C31—C29115.8 (3)
C7—C8—C10124.8 (3)C33—C32—N7105.6 (3)
N1—C8—C10124.3 (3)C33—C32—C35130.2 (3)
C1—C9—H9A109.5N7—C32—C35124.2 (3)
C1—C9—H9B109.5C32—C33—C34107.1 (3)
H9A—C9—H9B109.5C32—C33—H33126.5
C1—C9—H9C109.5C34—C33—H33126.5
H9A—C9—H9C109.5N8—C34—C33111.5 (3)
H9B—C9—H9C109.5N8—C34—C36120.2 (3)
O1—C10—N2119.0 (3)C33—C34—C36128.2 (3)
O1—C10—C8124.8 (3)C32—C35—H35A109.5
N2—C10—C8116.2 (3)C32—C35—H35B109.5
C12—C11—N2105.7 (3)H35A—C35—H35B109.5
C12—C11—C14130.2 (3)C32—C35—H35C109.5
N2—C11—C14123.9 (3)H35A—C35—H35C109.5
C11—C12—C13107.8 (3)H35B—C35—H35C109.5
C11—C12—H12126.1C34—C36—H36A109.5
C13—C12—H12126.1C34—C36—H36B109.5
N3—C13—C12109.2 (3)H36A—C36—H36B109.5
N3—C13—C15121.0 (3)C34—C36—H36C109.5
C12—C13—C15129.8 (3)H36A—C36—H36C109.5
C11—C14—H14A109.5H36B—C36—H36C109.5
C11—C14—H14B109.5O4—C37—N9116.9 (3)
H14A—C14—H14B109.5O4—C37—C27122.8 (3)
C11—C14—H14C109.5N9—C37—C27120.3 (2)
H14A—C14—H14C109.5C39—C38—N9105.1 (3)
H14B—C14—H14C109.5C39—C38—C41129.1 (3)
C13—C15—H15A109.5N9—C38—C41125.9 (3)
C13—C15—H15B109.5C38—C39—C40107.9 (3)
H15A—C15—H15B109.5C38—C39—H39126.1
C13—C15—H15C109.5C40—C39—H39126.1
H15A—C15—H15C109.5N10—C40—C39110.7 (3)
H15B—C15—H15C109.5N10—C40—C42119.4 (3)
O2—C16—C6123.8 (3)C39—C40—C42129.8 (3)
O2—C16—N4116.6 (3)C38—C41—H41A109.5
C6—C16—N4119.6 (3)C38—C41—H41B109.5
C18—C17—N4104.9 (3)H41A—C41—H41B109.5
C18—C17—C20130.0 (3)C38—C41—H41C109.5
N4—C17—C20125.1 (3)H41A—C41—H41C109.5
C17—C18—C19107.4 (3)H41B—C41—H41C109.5
C17—C18—H18126.3C40—C42—H42A109.5
C19—C18—H18126.3C40—C42—H42B109.5
N5—C19—C18111.4 (3)H42A—C42—H42B109.5
N5—C19—C21119.3 (3)C40—C42—H42C109.5
C18—C19—C21129.3 (3)H42A—C42—H42C109.5
C17—C20—H20A109.5H42B—C42—H42C109.5
C17—C20—H20B109.5C1—N1—C8130.1 (3)
H20A—C20—H20B109.5C1—N1—C5121.7 (3)
C17—C20—H20C109.5C8—N1—C5107.7 (2)
H20A—C20—H20C109.5N3—N2—C11111.1 (3)
H20B—C20—H20C109.5N3—N2—C10121.7 (3)
C19—C21—H21A109.5C11—N2—C10127.1 (3)
C19—C21—H21B109.5C13—N3—N2106.1 (3)
H21A—C21—H21B109.5N5—N4—C17112.2 (2)
C19—C21—H21C109.5N5—N4—C16120.7 (2)
H21A—C21—H21C109.5C17—N4—C16127.1 (3)
H21B—C21—H21C109.5C19—N5—N4104.1 (2)
C23—C22—N6117.2 (3)C22—N6—C26121.9 (2)
C23—C22—C30121.5 (3)C22—N6—C29129.9 (2)
N6—C22—C30121.1 (3)C26—N6—C29107.7 (2)
C22—C23—C24122.1 (3)N8—N7—C32110.7 (2)
C22—C23—H23118.9N8—N7—C31121.4 (2)
C24—C23—H23118.9C32—N7—C31127.8 (3)
C25—C24—C23120.1 (3)C34—N8—N7105.0 (2)
C25—C24—H24120.0N10—N9—C38110.8 (2)
C23—C24—H24120.0N10—N9—C37120.7 (2)
C24—C25—C26119.9 (3)C38—N9—C37128.5 (2)
C24—C25—H25120.0C40—N10—N9105.5 (2)
N1—C1—C2—C35.0 (5)C7—C8—N1—C51.3 (3)
C9—C1—C2—C3172.0 (3)C10—C8—N1—C5156.7 (3)
C1—C2—C3—C41.7 (5)C4—C5—N1—C15.9 (4)
C2—C3—C4—C54.7 (4)C6—C5—N1—C1172.6 (2)
C3—C4—C5—N11.0 (4)C4—C5—N1—C8179.0 (3)
C3—C4—C5—C6179.0 (3)C6—C5—N1—C80.5 (3)
C4—C5—C6—C7177.7 (3)C12—C11—N2—N32.8 (4)
N1—C5—C6—C70.4 (3)C14—C11—N2—N3178.4 (3)
C4—C5—C6—C162.8 (5)C12—C11—N2—C10179.1 (3)
N1—C5—C6—C16179.1 (3)C14—C11—N2—C105.3 (5)
C5—C6—C7—C81.3 (3)O1—C10—N2—N3163.3 (3)
C16—C6—C7—C8178.2 (3)C8—C10—N2—N319.4 (4)
C6—C7—C8—N11.6 (3)O1—C10—N2—C1112.6 (5)
C6—C7—C8—C10156.2 (3)C8—C10—N2—C11164.6 (3)
C7—C8—C10—O1132.8 (3)C12—C13—N3—N20.4 (3)
N1—C8—C10—O121.3 (5)C15—C13—N3—N2179.7 (3)
C7—C8—C10—N244.2 (4)C11—N2—N3—C132.0 (3)
N1—C8—C10—N2161.7 (3)C10—N2—N3—C13178.5 (3)
N2—C11—C12—C132.4 (4)C18—C17—N4—N50.6 (3)
C14—C11—C12—C13177.6 (3)C20—C17—N4—N5178.5 (3)
C11—C12—C13—N31.3 (4)C18—C17—N4—C16179.4 (3)
C11—C12—C13—C15178.6 (3)C20—C17—N4—C161.5 (5)
C7—C6—C16—O2176.7 (3)O2—C16—N4—N5170.5 (3)
C5—C6—C16—O22.6 (5)C6—C16—N4—N58.6 (4)
C7—C6—C16—N42.3 (5)O2—C16—N4—C179.5 (4)
C5—C6—C16—N4178.3 (3)C6—C16—N4—C17171.4 (3)
N4—C17—C18—C190.3 (3)C18—C19—N5—N40.4 (3)
C20—C17—C18—C19178.7 (3)C21—C19—N5—N4180.0 (3)
C17—C18—C19—N50.1 (4)C17—N4—N5—C190.6 (3)
C17—C18—C19—C21179.6 (3)C16—N4—N5—C19179.4 (2)
N6—C22—C23—C243.7 (4)C23—C22—N6—C268.6 (4)
C30—C22—C23—C24170.9 (3)C30—C22—N6—C26166.0 (3)
C22—C23—C24—C252.3 (5)C23—C22—N6—C29178.7 (3)
C23—C24—C25—C263.5 (5)C30—C22—N6—C294.1 (4)
C24—C25—C26—N61.2 (5)C25—C26—N6—C227.5 (4)
C24—C25—C26—C27177.0 (3)C27—C26—N6—C22171.2 (2)
N6—C26—C27—C280.6 (3)C25—C26—N6—C29179.5 (3)
C25—C26—C27—C28178.9 (3)C27—C26—N6—C290.8 (3)
N6—C26—C27—C37176.4 (3)C28—C29—N6—C22170.4 (3)
C25—C26—C27—C375.3 (5)C31—C29—N6—C2231.7 (4)
C26—C27—C28—C290.1 (3)C28—C29—N6—C260.8 (3)
C37—C27—C28—C29175.2 (3)C31—C29—N6—C26157.1 (3)
C27—C28—C29—N60.4 (3)C33—C32—N7—N80.6 (4)
C27—C28—C29—C31156.4 (3)C35—C32—N7—N8179.7 (3)
C28—C29—C31—O3128.1 (4)C33—C32—N7—C31178.3 (3)
N6—C29—C31—O325.6 (5)C35—C32—N7—C311.5 (5)
C28—C29—C31—N747.0 (4)O3—C31—N7—N8168.8 (3)
N6—C29—C31—N7159.3 (3)C29—C31—N7—N815.8 (4)
N7—C32—C33—C340.6 (4)O3—C31—N7—C329.9 (5)
C35—C32—C33—C34179.7 (3)C29—C31—N7—C32165.4 (3)
C32—C33—C34—N80.4 (4)C33—C34—N8—N70.0 (4)
C32—C33—C34—C36178.3 (3)C36—C34—N8—N7178.1 (3)
C28—C27—C37—O4172.3 (3)C32—N7—N8—C340.3 (3)
C26—C27—C37—O42.2 (5)C31—N7—N8—C34178.6 (3)
C28—C27—C37—N98.3 (5)C39—C38—N9—N101.2 (3)
C26—C27—C37—N9177.1 (3)C41—C38—N9—N10179.3 (3)
N9—C38—C39—C401.4 (3)C39—C38—N9—C37179.0 (3)
C41—C38—C39—C40179.2 (3)C41—C38—N9—C371.5 (5)
C38—C39—C40—N101.2 (4)O4—C37—N9—N10178.2 (3)
C38—C39—C40—C42179.9 (3)C27—C37—N9—N101.1 (4)
C2—C1—N1—C8179.8 (3)O4—C37—N9—C384.1 (5)
C9—C1—N1—C83.1 (4)C27—C37—N9—C38176.5 (3)
C2—C1—N1—C58.8 (4)C39—C40—N10—N90.4 (3)
C9—C1—N1—C5168.3 (3)C42—C40—N10—N9179.3 (3)
C7—C8—N1—C1171.1 (3)C38—N9—N10—C400.5 (3)
C10—C8—N1—C131.0 (5)C37—N9—N10—C40178.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O2i0.932.373.282 (4)167
C21—H21B···O1ii0.962.593.404 (4)142
C30—H30C···N3iii0.962.523.472 (4)169
C33—H33···O4iv0.932.553.393 (4)152
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z1/2; (iii) x1/2, y+1, z; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC21H21N5O2
Mr375.43
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)291
a, b, c (Å)19.7286 (11), 11.5659 (14), 17.8088 (18)
V3)4063.6 (7)
Z8
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.26 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.979, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
30693, 7955, 6221
Rint0.025
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.129, 1.07
No. of reflections7955
No. of parameters516
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.25

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O2i0.932.373.282 (4)167
C21—H21B···O1ii0.962.593.404 (4)142
C30—H30C···N3iii0.962.523.472 (4)169
C33—H33···O4iv0.932.553.393 (4)152
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z1/2; (iii) x1/2, y+1, z; (iv) x, y+1, z.
 

Acknowledgements

We thank the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for financial support.

References

First citationBruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationGu, W.-J., Zhuang, J., Jiang, Y.-L. & Wang, B.-X. (2011). Acta Cryst. E67, o123.  Web of Science CrossRef IUCr Journals
First citationJagerovic, N., Cano, C., Elguero, J. & Goya, P. (2002). Bioorg. Med. Chem. 10, 817–827.  Web of Science CrossRef PubMed CAS
First citationJames, D. A., Koya, K., Li, H., Liang, G. Q., Xia, Z. Q., Ying, W. W., Wu, Y. M. & Sun, L. J. (2008). Bioorg. Med. Chem. Lett. 18, 1784–1787.  Web of Science CrossRef PubMed CAS
First citationMcDonald, E., Workman, P. & Jones, K. (2006). Curr. Top. Med. Chem. 6, 1091–1107.  Web of Science CrossRef PubMed CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationShen, Y.-M., Wang, B.-X., Feng, Y.-Y., Shen, Z.-Y., Shen, J., Li, C. & Hu, H.-W. (2006). Chem. J. Chin. Univ. Chin. 27, 651–653.  CAS
First citationShen, Z.-Y., Wang, B.-X., Shen, J. & Hu, H.-W. (2008). Chem. J. Chin. Univ. Chin. 29, 916–918.  CAS
First citationTeklu, S., Gundersen, L. L., Larsen, T., Malterud, K. E. & Rise, F. (2005). Bioorg. Med. Chem. 13, 3127–3139.  Web of Science CrossRef PubMed CAS
First citationTukulula, M., Klein, R. & Kaye, P. T. (2010). Synth. Commun. 40, 2018–2028.  Web of Science CrossRef CAS
First citationWang, B.-X., Hu, J.-X., Zhang, X.-C., Hu, Y.-F. & Hu, H.-W. (2000). J. Heterocycl Chem. 37, 1533–1537.   CrossRef CAS

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds