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Acta Cryst. (2008). E64, o561    [ doi:10.1107/S1600536808003486 ]

N'-tert-Butyl-5-(4-chlorophenyl)furan-2-carbohydrazide

X.-C. Li, Y. Li, Z.-N. Cui, X.-L. Yang and Y. Ling

Abstract top

In the title molecule, C15H17ClN2O2, the furan and benzene rings form a dihedral angle of 15.35 (8)°. In the crystal structure, intermolecular N-H...O hydrogen bonds link the molecules into chains extended in the [010] direction.

Comment top

As one of molting hormone analogs, symmetrical N'-tert-butyl-N,N'-dibenzoylhydrazine (RH-5849) was first found to be a nonsteroidal ecdysone agonist in 1988 (Wing, 1988; Wing et al., 1988). Afterward, several diacylhydrazine compounds were commercially developed as insect growth regulators (IGRs) which were widely used in agriculture (Dhadialla et al., 1998; Heller et al., 1992; Mao et al., 2004). Recently, we synthesized a series of di- or mono- acylhydrazines containing furan for further study on the structure-activity relationship between monoacylhydrazines and diacylhydrazines. It was found that they both had good insecticidal activities (Yang et al., 2002; Li et al., 2006). In order to study the structural character and conformation of the monoacylhydrazine containing furan, the crystal structure of the title compound, (I), has been determined.

In (I) (Fig. 1), the benzene (C1—C6) and furan (O1/C7—C10) rings form a dihedral angle of 15.35 (8)°. The carbonyl group attached to the furan ring is almost coplanar with it. In the crystal, the intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains extended in direction [010].

Related literature top

For general background, see: Wing (1988); Wing et al. (1988); Dhadialla et al. (1998); Heller et al. (1992); Mao et al. (2004). For details of some monoacylhydrazines and diacylhydrazines containing furan, see: Yang et al. (2002); Li et al. (2006).

Experimental top

The title compound, (I), was synthesized by the reaction of 5-(4-chlorophenyl)furan-2-carbonyl chloride (0.96 g, 4 mmol) with tert-butylhydrazine hydrochloride (1.99 g, 16 mmol) using sodium hydroxide (10%, 8.0 g, 20 mmol) as the acid-binding agent. The mixture was stirred at room temperature for 5 h and filtered to obtain a yellow solution. Then the organic phase was separated and dried with anhydrous magnesium sulfate overnight. After removal of the solvent, the residue was purified by vacuum column chromatography on silica gel with petroleum ether and ethyl acetate as the eluent (V petroleum ether: V ethyl acetate = 3:1) and then recrystallized from hexane–ethyl acetate (Vhexane: Vethyl acetate= 1:1) to give colourless crystals suitable for X-ray diffraction (Li et al., 2006).

Refinement top

Atoms H1A and H2A were located on a difference map and isotropically refined. The rest H atoms were positioned geometrically (C—H = 0.95–0.98 Å), and refined using a riding model, with Uiso(H) = 1.2 or 1.5 Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
N'-tert-Butyl-5-(4-chlorophenyl)furan-2-carbohydrazide top
Crystal data top
C15H17ClN2O2Dx = 1.323 Mg m−3
Mr = 292.76Mo Kα radiation
λ = 0.71070 Å
Orthorhombic, P212121Cell parameters from 3053 reflections
a = 9.3770 (7) Åθ = 2.5–25.0º
b = 9.7861 (7) ŵ = 0.26 mm−1
c = 16.0119 (12) ÅT = 113 (2) K
V = 1469.32 (19) Å3Prism, colourless
Z = 40.32 × 0.24 × 0.20 mm
F000 = 616
Data collection top
Rigaku Saturn
diffractometer		3496 independent reflections
Radiation source: rotating anode2754 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.039
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 2.4º
ω scansh = −12→12
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −12→12
Tmin = 0.921, Tmax = 0.949l = −21→21
13814 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.027  w = 1/[σ2(Fo2) + (0.0232P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max = 0.001
S = 0.96Δρmax = 0.22 e Å−3
3496 reflectionsΔρmin = −0.21 e Å−3
192 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1490 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (4)
Crystal data top
C15H17ClN2O2V = 1469.32 (19) Å3
Mr = 292.76Z = 4
Orthorhombic, P212121Mo Kα
a = 9.3770 (7) ŵ = 0.26 mm−1
b = 9.7861 (7) ÅT = 113 (2) K
c = 16.0119 (12) Å0.32 × 0.24 × 0.20 mm
Data collection top
Rigaku Saturn
diffractometer		3496 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		2754 reflections with I > 2σ(I)
Tmin = 0.921, Tmax = 0.949Rint = 0.039
13814 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.056Δρmax = 0.22 e Å−3
S = 0.96Δρmin = −0.21 e Å−3
3496 reflectionsAbsolute structure: Flack (1983), 1490 Friedel pairs
192 parametersFlack parameter: 0.00 (4)
Special details top

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) top
xyzUiso*/Ueq
Cl11.32887 (4)0.17773 (4)1.09957 (2)0.02303 (9)
O11.13067 (10)0.70996 (9)0.86903 (6)0.0151 (2)
O20.98638 (10)0.97666 (9)0.74249 (6)0.0174 (2)
N10.91782 (13)0.75551 (12)0.76336 (7)0.0151 (3)
N20.80263 (13)0.76074 (12)0.70613 (7)0.0146 (3)
C11.30520 (15)0.33360 (15)1.04901 (8)0.0159 (3)
C21.17767 (16)0.35872 (14)1.00795 (8)0.0168 (3)
H21.10400.29211.00780.020*
C31.15907 (16)0.48241 (13)0.96720 (8)0.0159 (3)
H31.07200.50020.93890.019*
C41.26701 (15)0.58168 (15)0.96708 (9)0.0149 (3)
C51.39448 (15)0.55382 (14)1.00941 (8)0.0176 (3)
H51.46850.62011.01000.021*
C61.41381 (15)0.43007 (14)1.05056 (9)0.0175 (3)
H61.50030.41171.07940.021*
C71.24400 (15)0.71056 (14)0.92346 (8)0.0153 (3)
C81.30641 (15)0.83596 (15)0.92271 (8)0.0175 (3)
H81.38680.86350.95470.021*
C91.22900 (14)0.91848 (15)0.86505 (9)0.0165 (3)
H91.24721.01130.85150.020*
C101.12421 (14)0.83819 (14)0.83345 (8)0.0137 (3)
C111.00485 (15)0.86322 (14)0.77523 (8)0.0138 (3)
C120.66234 (15)0.78352 (14)0.74892 (9)0.0163 (3)
C130.65461 (17)0.92221 (15)0.79274 (9)0.0240 (4)
H13A0.72830.92700.83600.036*
H13B0.56040.93330.81840.036*
H13C0.67010.99520.75180.036*
C140.55159 (16)0.77717 (16)0.67895 (10)0.0241 (4)
H14A0.57130.84910.63800.036*
H14B0.45610.79060.70250.036*
H14C0.55630.68770.65160.036*
C150.63850 (16)0.66767 (15)0.81165 (9)0.0230 (3)
H15A0.65010.57950.78340.035*
H15B0.54190.67420.83470.035*
H15C0.70830.67510.85700.035*
H2A0.8186 (15)0.8364 (13)0.6731 (8)0.012 (4)*
H1A0.9484 (16)0.6722 (16)0.7743 (9)0.029 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02355 (19)0.02007 (19)0.0255 (2)0.00437 (17)−0.00042 (17)0.00723 (17)
O10.0162 (5)0.0122 (5)0.0169 (5)0.0000 (4)−0.0040 (4)0.0010 (4)
O20.0205 (5)0.0104 (5)0.0214 (5)−0.0001 (4)−0.0019 (5)0.0019 (4)
N10.0154 (6)0.0107 (7)0.0192 (7)0.0012 (5)−0.0047 (5)0.0004 (5)
N20.0145 (7)0.0146 (7)0.0146 (6)0.0003 (5)−0.0032 (5)0.0022 (5)
C10.0218 (8)0.0154 (7)0.0105 (7)0.0048 (7)0.0022 (6)0.0016 (6)
C20.0168 (7)0.0180 (8)0.0157 (7)−0.0019 (6)0.0012 (7)−0.0011 (6)
C30.0146 (7)0.0187 (8)0.0144 (7)0.0016 (6)−0.0031 (6)−0.0010 (6)
C40.0157 (7)0.0162 (8)0.0128 (7)0.0021 (6)−0.0004 (6)−0.0034 (6)
C50.0180 (8)0.0172 (8)0.0177 (8)−0.0014 (6)−0.0022 (6)−0.0043 (6)
C60.0157 (8)0.0225 (8)0.0144 (8)0.0045 (7)−0.0029 (6)−0.0021 (6)
C70.0125 (7)0.0185 (8)0.0150 (8)0.0015 (6)−0.0024 (6)−0.0025 (6)
C80.0137 (7)0.0185 (7)0.0202 (8)−0.0026 (6)−0.0021 (6)−0.0018 (6)
C90.0169 (7)0.0129 (7)0.0196 (8)−0.0008 (6)0.0022 (6)0.0011 (6)
C100.0157 (7)0.0106 (7)0.0149 (7)0.0023 (6)0.0015 (6)0.0004 (6)
C110.0139 (7)0.0139 (8)0.0137 (7)0.0019 (6)0.0041 (6)−0.0023 (6)
C120.0134 (7)0.0168 (7)0.0187 (8)0.0007 (6)−0.0017 (7)0.0000 (6)
C130.0207 (9)0.0222 (8)0.0292 (9)0.0024 (7)−0.0007 (7)−0.0052 (7)
C140.0209 (8)0.0245 (9)0.0270 (9)0.0008 (7)−0.0075 (7)0.0012 (7)
C150.0224 (8)0.0230 (8)0.0237 (8)−0.0003 (8)−0.0005 (7)0.0029 (7)
Geometric parameters (Å, °) top
Cl1—C11.7411 (14)C6—H60.9500
O1—C71.3744 (15)C7—C81.360 (2)
O1—C101.3795 (16)C8—C91.4252 (19)
O2—C111.2398 (15)C8—H80.9500
N1—C111.3465 (17)C9—C101.3561 (18)
N1—N21.4174 (16)C9—H90.9500
N1—H1A0.882 (15)C10—C111.4771 (19)
N2—C121.4999 (18)C12—C141.5289 (19)
N2—H2A0.922 (13)C12—C131.5296 (18)
C1—C21.3866 (19)C12—C151.5311 (18)
C1—C61.3889 (19)C13—H13A0.9800
C2—C31.3861 (17)C13—H13B0.9800
C2—H20.9500C13—H13C0.9800
C3—C41.4029 (19)C14—H14A0.9800
C3—H30.9500C14—H14B0.9800
C4—C51.4009 (18)C14—H14C0.9800
C4—C71.4578 (19)C15—H15A0.9800
C5—C61.3906 (19)C15—H15B0.9800
C5—H50.9500C15—H15C0.9800
C7—O1—C10106.97 (10)C10—C9—H9126.8
C11—N1—N2121.66 (12)C8—C9—H9126.8
C11—N1—H1A119.9 (10)C9—C10—O1109.95 (12)
N2—N1—H1A114.2 (10)C9—C10—C11133.51 (13)
N1—N2—C12112.24 (10)O1—C10—C11116.41 (12)
N1—N2—H2A106.0 (9)O2—C11—N1123.82 (13)
C12—N2—H2A106.6 (9)O2—C11—C10121.41 (13)
C2—C1—C6121.36 (13)N1—C11—C10114.74 (12)
C2—C1—Cl1119.06 (11)N2—C12—C14104.77 (11)
C6—C1—Cl1119.58 (11)N2—C12—C13112.52 (12)
C3—C2—C1119.11 (13)C14—C12—C13109.88 (12)
C3—C2—H2120.4N2—C12—C15108.52 (11)
C1—C2—H2120.4C14—C12—C15110.58 (12)
C2—C3—C4120.97 (14)C13—C12—C15110.44 (12)
C2—C3—H3119.5C12—C13—H13A109.5
C4—C3—H3119.5C12—C13—H13B109.5
C5—C4—C3118.69 (13)H13A—C13—H13B109.5
C5—C4—C7121.77 (13)C12—C13—H13C109.5
C3—C4—C7119.54 (13)H13A—C13—H13C109.5
C6—C5—C4120.66 (13)H13B—C13—H13C109.5
C6—C5—H5119.7C12—C14—H14A109.5
C4—C5—H5119.7C12—C14—H14B109.5
C1—C6—C5119.20 (13)H14A—C14—H14B109.5
C1—C6—H6120.4C12—C14—H14C109.5
C5—C6—H6120.4H14A—C14—H14C109.5
C8—C7—O1109.33 (12)H14B—C14—H14C109.5
C8—C7—C4136.18 (13)C12—C15—H15A109.5
O1—C7—C4114.49 (12)C12—C15—H15B109.5
C7—C8—C9107.33 (13)H15A—C15—H15B109.5
C7—C8—H8126.3C12—C15—H15C109.5
C9—C8—H8126.3H15A—C15—H15C109.5
C10—C9—C8106.41 (13)H15B—C15—H15C109.5
C11—N1—N2—C12−101.13 (14)O1—C7—C8—C9−0.05 (16)
C6—C1—C2—C30.5 (2)C4—C7—C8—C9−179.46 (15)
Cl1—C1—C2—C3−179.57 (10)C7—C8—C9—C10−0.42 (16)
C1—C2—C3—C40.0 (2)C8—C9—C10—O10.73 (16)
C2—C3—C4—C5−0.3 (2)C8—C9—C10—C11176.25 (14)
C2—C3—C4—C7179.88 (13)C7—O1—C10—C9−0.77 (15)
C3—C4—C5—C60.2 (2)C7—O1—C10—C11−177.14 (11)
C7—C4—C5—C6180.00 (13)N2—N1—C11—O25.2 (2)
C2—C1—C6—C5−0.6 (2)N2—N1—C11—C10−176.72 (11)
Cl1—C1—C6—C5179.45 (10)C9—C10—C11—O21.9 (2)
C4—C5—C6—C10.3 (2)O1—C10—C11—O2177.18 (12)
C10—O1—C7—C80.49 (14)C9—C10—C11—N1−176.21 (15)
C10—O1—C7—C4−179.95 (11)O1—C10—C11—N1−0.92 (17)
C5—C4—C7—C8−15.6 (3)N1—N2—C12—C14−176.55 (11)
C3—C4—C7—C8164.26 (16)N1—N2—C12—C1364.11 (15)
C5—C4—C7—O1165.04 (12)N1—N2—C12—C15−58.41 (14)
C3—C4—C7—O1−15.13 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882 (15)2.026 (16)2.8744 (15)160.9 (14)
Symmetry codes: (i) −x+2, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882 (15)2.026 (16)2.8744 (15)160.9 (14)
Symmetry codes: (i) −x+2, y−1/2, −z+3/2.
Acknowledgements top

This work was supported by the National Basic Research Program of China (grant No. 2003CB114405), the National Natural Science Foundation of China (grant No. 20672138) and the National High Technology Research and Development Program of China (grant No. 2006 A A10A201). The authors also thank the State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, People's Republic of China.

references
References top

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