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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o8.
Published online 2007 December 6. doi:  10.1107/S1600536807061089
PMCID: PMC2914898

3-tert-Butyl-4-oxo-3,4-dihydro­phthalazin-1-yl 3,5-dimethyl­benzoate

Abstract

The title compound, C21H22N2O3, was synthesized by the reaction of tert-butyl­hydrazine with phthalic anhydride and further O-benzoyl­ation of the resulting inter­mediate by 3,5-dimethyl­benzoyl chloride. Inter­molecular C—H(...)O=C inter­actions link the mol­ecules into layers.

Related literature

For ecdysone agonists, see: Wing (1988 [triangle]). For the synthesis, see: Hou et al. (2002 [triangle]). For C—N bond lengths, see: Sasada (1984 [triangle]).

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Object name is e-64-000o8-scheme1.jpg

Experimental

Crystal data

  • C21H22N2O3
  • M r = 350.41
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-000o8-efi1.jpg
  • a = 8.7974 (2) Å
  • b = 18.7622 (4) Å
  • c = 11.7405 (3) Å
  • β = 92.634 (2)°
  • V = 1935.82 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 296 (2) K
  • 0.54 × 0.52 × 0.48 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 14969 measured reflections
  • 3804 independent reflections
  • 2879 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.137
  • S = 1.06
  • 3804 reflections
  • 241 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807061089/ln2004sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061089/ln2004Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the National Eleventh–Five Key Project of the People’s Republic of China (2006BAE01A01-4).

supplementary crystallographic information

Comment

DibendzoyIhydrazines insect growth regulators are well known as nonsteroidal ecdysone agonists, which induce prematurely abnormal and ultimately lethal larval molting (Wing, 1988). The title compound, (I), was obtained unintentionally as the product of an attempted synthesis of a dibendzoylhydrazine and we present its crystal structure here. The molecular structure of (I) is shown in Fig.1. The bond length of C18—N2 [1.517 (2) Å] is slightly greater than the normal value of C—N [1.47 Å; Sasada, 1984] because of the larger terminal group tert-butyl moiety. The crystal structure of (I) also involves two weak C—H···O?C hydrogen-bonding interactions, which link the molecules into layers which lie parallel to the (101) plane. (Fig. 2 and Table 1).

Experimental

Phthalic anhydride (0.015 mol) was heated to 323 K in acetic acid, tert-butyldrazine (0.015 mol) was added dropwise, the solution was stirred for 3 h at 383 K. Then the mixture was condensed and washed with water and filtered, which afforded 2-tert-butyl-4-hydroxyphthalazin-1(2H)-one (m.p. 391–393 K). This compound (0.01 mol) was heated to 333 K in butyl acetate (30 ml) and water (20 ml) in the presence of DMPA catalyst (0.1 g), 3,5-Dimethylbenzoyl chloride (0.01 mol) and a saturated solution of Na2CO3(0.02 mol) which were added dropwise, then the mixture reacted for 4 h (Hou et al., 2002). The solution was cooled, washed with water and dried. The product was concentrated and purified by column chromatography (silica gel, petroleum ether-acetate 10:1) to give the title compound, (I) (yield 46%, m.p. 421–422 K). 1H NMR (CDCl3, δ, p.p.m): 1.71 (9H, s), 2.43 (6H, s), 7.33–7.26 (1H, s), 7.74–7.57 (1H, s), 7.79–7.75 (2H, m), 7.90–7.89 (2H, s), 8.46–8.43 (1H, m). Compound (I) was recrystallized from ethyl acetate. Single crystals of (I), suitable for X-ray analysis, were grown by natural evaporation of the solvent.

Refinement

The C—H atoms were constrained to an ideal geometry, with C(methyl)—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C), and C(phenyl)—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Fig. 2.
The crystal structure of (I), viewed along the a axis. The dashed lines indicate C—H···O interations.

Crystal data

C21H22N2O3F000 = 744
Mr = 350.41Dx = 1.202 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4673 reflections
a = 8.7974 (2) Åθ = 2.6–26.8º
b = 18.7622 (4) ŵ = 0.08 mm1
c = 11.7405 (3) ÅT = 296 (2) K
β = 92.634 (2)ºBlock, colourless
V = 1935.82 (8) Å30.54 × 0.52 × 0.48 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2879 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Monochromator: graphiteθmax = 26.0º
T = 296(2) Kθmin = 2.2º
phi and ω scansh = −8→10
Absorption correction: nonek = −23→23
14969 measured reflectionsl = −14→14
3804 independent reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0654P)2 + 0.3695P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.137(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.23 e Å3
3804 reflectionsΔρmin = −0.21 e Å3
241 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.020 (2)
Secondary atom site location: difference Fourier map

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 (Å2)

xyzUiso*/Ueq
C1−0.1890 (3)−0.01591 (13)0.3028 (2)0.0934 (7)
H1A−0.2610−0.01370.23890.140*
H1B−0.2406−0.00800.37200.140*
H1C−0.1417−0.06200.30550.140*
C2−0.06900 (19)0.04061 (9)0.29032 (15)0.0586 (4)
C3−0.0157 (2)0.08071 (10)0.38294 (14)0.0628 (5)
H3−0.05470.07200.45390.075*
C40.0936 (2)0.13334 (9)0.37380 (13)0.0563 (4)
C50.1455 (3)0.17747 (12)0.47572 (16)0.0809 (6)
H5A0.07570.17140.53540.121*
H5B0.14870.22680.45430.121*
H5C0.24520.16230.50220.121*
C60.15174 (18)0.14558 (8)0.26761 (13)0.0484 (4)
H60.22630.18010.25940.058*
C70.09907 (16)0.10652 (8)0.17396 (12)0.0438 (3)
C8−0.01108 (17)0.05444 (9)0.18535 (14)0.0509 (4)
H8−0.04610.02870.12180.061*
C90.15521 (17)0.11830 (8)0.05858 (13)0.0463 (4)
C100.33337 (17)0.17600 (8)−0.04896 (12)0.0468 (4)
C110.26329 (16)0.22905 (8)−0.12040 (12)0.0463 (4)
C120.14226 (19)0.27236 (10)−0.09065 (14)0.0578 (4)
H120.10170.2681−0.01920.069*
C130.0840 (2)0.32105 (11)−0.16753 (17)0.0676 (5)
H130.00350.3500−0.14780.081*
C140.1433 (2)0.32802 (10)−0.27457 (17)0.0662 (5)
H140.10150.3610−0.32620.079*
C150.26313 (19)0.28648 (9)−0.30426 (14)0.0561 (4)
H150.30340.2916−0.37570.067*
C160.32475 (16)0.23645 (8)−0.22752 (12)0.0465 (4)
C170.45363 (18)0.19228 (9)−0.25804 (13)0.0536 (4)
C180.65359 (19)0.10239 (10)−0.19097 (16)0.0624 (5)
C190.6200 (3)0.04906 (15)−0.2852 (2)0.1083 (9)
H19A0.71140.0237−0.30110.163*
H19B0.58300.0736−0.35260.163*
H19C0.54430.0160−0.26180.163*
C200.7848 (2)0.15067 (13)−0.2199 (3)0.0987 (8)
H20A0.80190.1851−0.16020.148*
H20B0.76030.1749−0.29040.148*
H20C0.87500.1226−0.22750.148*
C210.6985 (3)0.06425 (15)−0.0799 (2)0.1006 (8)
H21A0.79240.0391−0.08830.151*
H21B0.62020.0310−0.06190.151*
H21C0.71120.0986−0.01960.151*
N10.44872 (15)0.13807 (7)−0.07117 (11)0.0521 (3)
N20.51350 (15)0.14770 (7)−0.17419 (11)0.0531 (4)
O10.10477 (15)0.09179 (7)−0.02755 (9)0.0687 (4)
O20.27700 (12)0.16353 (6)0.05844 (8)0.0525 (3)
O30.50744 (16)0.19522 (9)−0.35226 (10)0.0811 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0836 (15)0.1065 (17)0.0913 (15)−0.0374 (13)0.0168 (12)0.0187 (13)
C20.0530 (9)0.0635 (10)0.0599 (10)−0.0050 (8)0.0100 (8)0.0118 (8)
C30.0667 (11)0.0748 (12)0.0481 (9)0.0025 (9)0.0174 (8)0.0133 (9)
C40.0660 (11)0.0594 (10)0.0438 (8)0.0052 (8)0.0057 (7)0.0035 (7)
C50.1118 (17)0.0858 (14)0.0454 (10)−0.0070 (12)0.0064 (10)−0.0040 (9)
C60.0504 (9)0.0490 (8)0.0461 (8)−0.0003 (7)0.0052 (6)0.0036 (7)
C70.0421 (8)0.0469 (8)0.0428 (7)0.0039 (6)0.0067 (6)0.0030 (6)
C80.0482 (9)0.0533 (9)0.0516 (9)−0.0023 (7)0.0051 (7)0.0016 (7)
C90.0461 (8)0.0484 (8)0.0448 (8)−0.0023 (6)0.0054 (6)−0.0002 (7)
C100.0441 (8)0.0591 (9)0.0379 (7)−0.0071 (7)0.0091 (6)−0.0019 (7)
C110.0410 (8)0.0560 (9)0.0423 (8)−0.0064 (6)0.0072 (6)−0.0055 (7)
C120.0516 (9)0.0696 (11)0.0533 (9)0.0013 (8)0.0153 (7)−0.0044 (8)
C130.0540 (10)0.0737 (12)0.0757 (12)0.0110 (9)0.0101 (9)−0.0027 (10)
C140.0611 (11)0.0718 (11)0.0650 (11)0.0046 (9)−0.0037 (9)0.0100 (9)
C150.0551 (10)0.0677 (10)0.0459 (8)−0.0044 (8)0.0046 (7)0.0018 (8)
C160.0420 (8)0.0576 (9)0.0401 (7)−0.0058 (7)0.0060 (6)−0.0031 (7)
C170.0480 (9)0.0685 (10)0.0452 (8)−0.0028 (8)0.0126 (7)−0.0021 (8)
C180.0509 (10)0.0663 (11)0.0710 (11)0.0090 (8)0.0148 (8)−0.0055 (9)
C190.0810 (16)0.1075 (18)0.136 (2)0.0210 (14)0.0026 (15)−0.0579 (17)
C200.0515 (12)0.0989 (17)0.148 (2)0.0077 (11)0.0250 (13)0.0081 (16)
C210.0916 (17)0.1129 (19)0.0984 (17)0.0488 (15)0.0183 (13)0.0172 (14)
N10.0488 (8)0.0610 (8)0.0472 (7)−0.0021 (6)0.0103 (6)0.0013 (6)
N20.0481 (8)0.0622 (8)0.0501 (7)0.0044 (6)0.0150 (6)0.0003 (6)
O10.0797 (9)0.0804 (9)0.0463 (6)−0.0271 (7)0.0065 (6)−0.0067 (6)
O20.0512 (6)0.0686 (7)0.0383 (5)−0.0120 (5)0.0102 (4)−0.0012 (5)
O30.0777 (9)0.1161 (11)0.0520 (7)0.0211 (8)0.0310 (6)0.0112 (7)

Geometric parameters (Å, °)

C1—C21.508 (3)C12—C131.367 (3)
C1—H1A0.9600C12—H120.9300
C1—H1B0.9600C13—C141.389 (3)
C1—H1C0.9600C13—H130.9300
C2—C81.380 (2)C14—C151.369 (2)
C2—C31.386 (3)C14—H140.9300
C3—C41.386 (2)C15—C161.393 (2)
C3—H30.9300C15—H150.9300
C4—C61.388 (2)C16—C171.462 (2)
C4—C51.509 (3)C17—O31.2243 (18)
C5—H5A0.9600C17—N21.378 (2)
C5—H5B0.9600C18—C191.511 (3)
C5—H5C0.9600C18—N21.517 (2)
C6—C71.383 (2)C18—C201.518 (3)
C6—H60.9300C18—C211.523 (3)
C7—C81.387 (2)C19—H19A0.9600
C7—C91.4796 (19)C19—H19B0.9600
C8—H80.9300C19—H19C0.9600
C9—O11.1939 (18)C20—H20A0.9600
C9—O21.3668 (18)C20—H20B0.9600
C10—N11.276 (2)C20—H20C0.9600
C10—O21.3958 (17)C21—H21A0.9600
C10—C111.424 (2)C21—H21B0.9600
C11—C161.3985 (19)C21—H21C0.9600
C11—C121.397 (2)N1—N21.3725 (17)
C2—C1—H1A109.5C12—C13—H13119.5
C2—C1—H1B109.5C14—C13—H13119.5
H1A—C1—H1B109.5C15—C14—C13120.16 (17)
C2—C1—H1C109.5C15—C14—H14119.9
H1A—C1—H1C109.5C13—C14—H14119.9
H1B—C1—H1C109.5C14—C15—C16120.01 (15)
C8—C2—C3118.23 (15)C14—C15—H15120.0
C8—C2—C1120.53 (17)C16—C15—H15120.0
C3—C2—C1121.24 (16)C15—C16—C11119.56 (14)
C2—C3—C4122.48 (15)C15—C16—C17120.42 (14)
C2—C3—H3118.8C11—C16—C17120.02 (14)
C4—C3—H3118.8O3—C17—N2121.47 (15)
C3—C4—C6118.23 (15)O3—C17—C16122.15 (16)
C3—C4—C5121.03 (16)N2—C17—C16116.37 (13)
C6—C4—C5120.73 (16)C19—C18—N2109.48 (15)
C4—C5—H5A109.5C19—C18—C20110.88 (19)
C4—C5—H5B109.5N2—C18—C20108.96 (15)
H5A—C5—H5B109.5C19—C18—C21110.5 (2)
C4—C5—H5C109.5N2—C18—C21109.42 (14)
H5A—C5—H5C109.5C20—C18—C21107.58 (19)
H5B—C5—H5C109.5C18—C19—H19A109.5
C7—C6—C4120.15 (15)C18—C19—H19B109.5
C7—C6—H6119.9H19A—C19—H19B109.5
C4—C6—H6119.9C18—C19—H19C109.5
C6—C7—C8120.43 (14)H19A—C19—H19C109.5
C6—C7—C9122.33 (13)H19B—C19—H19C109.5
C8—C7—C9117.24 (13)C18—C20—H20A109.5
C2—C8—C7120.47 (15)C18—C20—H20B109.5
C2—C8—H8119.8H20A—C20—H20B109.5
C7—C8—H8119.8C18—C20—H20C109.5
O1—C9—O2121.23 (13)H20A—C20—H20C109.5
O1—C9—C7125.91 (14)H20B—C20—H20C109.5
O2—C9—C7112.86 (12)C18—C21—H21A109.5
N1—C10—O2114.20 (14)C18—C21—H21B109.5
N1—C10—C11126.62 (13)H21A—C21—H21B109.5
O2—C10—C11119.16 (13)C18—C21—H21C109.5
C16—C11—C12119.86 (15)H21A—C21—H21C109.5
C16—C11—C10115.11 (13)H21B—C21—H21C109.5
C12—C11—C10125.03 (14)C10—N1—N2118.22 (13)
C13—C12—C11119.38 (15)N1—N2—C17123.30 (13)
C13—C12—H12120.3N1—N2—C18114.41 (13)
C11—C12—H12120.3C17—N2—C18122.24 (13)
C12—C13—C14121.03 (17)C9—O2—C10114.60 (11)
C8—C2—C3—C4−0.5 (3)C12—C11—C16—C15−0.8 (2)
C1—C2—C3—C4−179.50 (18)C10—C11—C16—C15179.37 (14)
C2—C3—C4—C6−0.4 (3)C12—C11—C16—C17178.66 (14)
C2—C3—C4—C5178.11 (18)C10—C11—C16—C17−1.1 (2)
C3—C4—C6—C70.9 (2)C15—C16—C17—O3−3.2 (3)
C5—C4—C6—C7−177.60 (16)C11—C16—C17—O3177.35 (16)
C4—C6—C7—C8−0.6 (2)C15—C16—C17—N2175.80 (14)
C4—C6—C7—C9178.92 (14)C11—C16—C17—N2−3.7 (2)
C3—C2—C8—C70.9 (2)O2—C10—N1—N2−178.84 (12)
C1—C2—C8—C7179.90 (17)C11—C10—N1—N2−0.7 (2)
C6—C7—C8—C2−0.4 (2)C10—N1—N2—C17−5.0 (2)
C9—C7—C8—C2−179.87 (14)C10—N1—N2—C18177.70 (14)
C6—C7—C9—O1−172.15 (16)O3—C17—N2—N1−174.04 (16)
C8—C7—C9—O17.3 (2)C16—C17—N2—N17.0 (2)
C6—C7—C9—O28.7 (2)O3—C17—N2—C183.0 (3)
C8—C7—C9—O2−171.80 (13)C16—C17—N2—C18−175.93 (14)
N1—C10—C11—C163.6 (2)C19—C18—N2—N1113.71 (19)
O2—C10—C11—C16−178.33 (13)C20—C18—N2—N1−124.88 (18)
N1—C10—C11—C12−176.22 (16)C21—C18—N2—N1−7.5 (2)
O2—C10—C11—C121.9 (2)C19—C18—N2—C17−63.6 (2)
C16—C11—C12—C130.8 (2)C20—C18—N2—C1757.8 (2)
C10—C11—C12—C13−179.44 (16)C21—C18—N2—C17175.19 (18)
C11—C12—C13—C140.0 (3)O1—C9—O2—C100.8 (2)
C12—C13—C14—C15−0.8 (3)C7—C9—O2—C10179.99 (12)
C13—C14—C15—C160.8 (3)N1—C10—O2—C9−97.91 (16)
C14—C15—C16—C110.1 (2)C11—C10—O2—C983.76 (17)
C14—C15—C16—C17−179.44 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8···O1i0.932.563.391 (2)149
C12—H12···O3ii0.932.273.149 (2)157

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LN2004).

References

  • Bruker (1997). SHELXTL Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2000). SMART (Version 5.059) and SAINT (Version 6.01). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hou, Z.-K., Ren, Y.-G. & Zhang, L.-J. (2002). Chin. J. Pestic. Sci.4, 72–74.
  • Sasada, Y. (1984). Molecular and Crystal Structure in Chemistry Handbook, 3rd ed. Tokyo: Maruzen Press/The Chemistry Society of Japan.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXS97 University of Göttingen, Germany.
  • Wing, K. D. (1988). Science, 241, 467–469. [PubMed]

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