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

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.057
• Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     -   C11     ..       5.21 su
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O2      ..       3.24 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  Cl1    ..  C11     ..       3.24 Ang.
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.04

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.88
           From the CIF: _reflns_number_total               3496
           Count of symmetry unique reflns         2012
           Completeness (_total/calc)            173.76%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1484
           Fraction of Friedel pairs measured     0.738
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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 (V_hexane: V_{ethyl acetate}= 1:1) to give colourless crystals suitable for X-ray diffraction (Li et al., 2006).

S3. Refinement

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 U_iso(H) = 1.2 or 1.5 U_eq(C).

Computing details

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

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

Crystal data

C15H17ClN2O2	Dx = 1.323 Mg m^−3
Mr = 292.76	Mo Kα radiation, λ = 0.71070 Å
Orthorhombic, P212121	Cell parameters from 3053 reflections
a = 9.3770 (7) Å	θ = 2.5–25.0°
b = 9.7861 (7) Å	µ = 0.26 mm^−1
c = 16.0119 (12) Å	T = 113 K
V = 1469.32 (19) Å^3	Prism, colourless
Z = 4	0.32 × 0.24 × 0.20 mm
F(000) = 616

Data collection

Rigaku Saturn diffractometer	3496 independent reflections
Radiation source: rotating anode	2754 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.039
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.4°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −12→12
Tmin = 0.921, Tmax = 0.949	l = −21→21
13814 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0232P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.001
3496 reflections	Δρmax = 0.22 e Å^−3
192 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1490 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (4)

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	1.32887 (4)	0.17773 (4)	1.09957 (2)	0.02303 (9)
O1	1.13067 (10)	0.70996 (9)	0.86903 (6)	0.0151 (2)
O2	0.98638 (10)	0.97666 (9)	0.74249 (6)	0.0174 (2)
N1	0.91782 (13)	0.75551 (12)	0.76336 (7)	0.0151 (3)
N2	0.80263 (13)	0.76074 (12)	0.70613 (7)	0.0146 (3)
C1	1.30520 (15)	0.33360 (15)	1.04901 (8)	0.0159 (3)
C2	1.17767 (16)	0.35872 (14)	1.00795 (8)	0.0168 (3)
H2	1.1040	0.2921	1.0078	0.020*
C3	1.15907 (16)	0.48241 (13)	0.96720 (8)	0.0159 (3)
H3	1.0720	0.5002	0.9389	0.019*
C4	1.26701 (15)	0.58168 (15)	0.96708 (9)	0.0149 (3)
C5	1.39448 (15)	0.55382 (14)	1.00941 (8)	0.0176 (3)
H5	1.4685	0.6201	1.0100	0.021*
C6	1.41381 (15)	0.43007 (14)	1.05056 (9)	0.0175 (3)
H6	1.5003	0.4117	1.0794	0.021*
C7	1.24400 (15)	0.71056 (14)	0.92346 (8)	0.0153 (3)
C8	1.30641 (15)	0.83596 (15)	0.92271 (8)	0.0175 (3)
H8	1.3868	0.8635	0.9547	0.021*
C9	1.22900 (14)	0.91848 (15)	0.86505 (9)	0.0165 (3)
H9	1.2472	1.0113	0.8515	0.020*
C10	1.12421 (14)	0.83819 (14)	0.83345 (8)	0.0137 (3)
C11	1.00485 (15)	0.86322 (14)	0.77523 (8)	0.0138 (3)
C12	0.66234 (15)	0.78352 (14)	0.74892 (9)	0.0163 (3)
C13	0.65461 (17)	0.92221 (15)	0.79274 (9)	0.0240 (4)
H13A	0.7283	0.9270	0.8360	0.036*
H13B	0.5604	0.9333	0.8184	0.036*
H13C	0.6701	0.9952	0.7518	0.036*
C14	0.55159 (16)	0.77717 (16)	0.67895 (10)	0.0241 (4)
H14A	0.5713	0.8491	0.6380	0.036*
H14B	0.4561	0.7906	0.7025	0.036*
H14C	0.5563	0.6877	0.6516	0.036*
C15	0.63850 (16)	0.66767 (15)	0.81165 (9)	0.0230 (3)
H15A	0.6501	0.5795	0.7834	0.035*
H15B	0.5419	0.6742	0.8347	0.035*
H15C	0.7083	0.6751	0.8570	0.035*
H2A	0.8186 (15)	0.8364 (13)	0.6731 (8)	0.012 (4)*
H1A	0.9484 (16)	0.6722 (16)	0.7743 (9)	0.029 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02355 (19)	0.02007 (19)	0.0255 (2)	0.00437 (17)	−0.00042 (17)	0.00723 (17)
O1	0.0162 (5)	0.0122 (5)	0.0169 (5)	0.0000 (4)	−0.0040 (4)	0.0010 (4)
O2	0.0205 (5)	0.0104 (5)	0.0214 (5)	−0.0001 (4)	−0.0019 (5)	0.0019 (4)
N1	0.0154 (6)	0.0107 (7)	0.0192 (7)	0.0012 (5)	−0.0047 (5)	0.0004 (5)
N2	0.0145 (7)	0.0146 (7)	0.0146 (6)	0.0003 (5)	−0.0032 (5)	0.0022 (5)
C1	0.0218 (8)	0.0154 (7)	0.0105 (7)	0.0048 (7)	0.0022 (6)	0.0016 (6)
C2	0.0168 (7)	0.0180 (8)	0.0157 (7)	−0.0019 (6)	0.0012 (7)	−0.0011 (6)
C3	0.0146 (7)	0.0187 (8)	0.0144 (7)	0.0016 (6)	−0.0031 (6)	−0.0010 (6)
C4	0.0157 (7)	0.0162 (8)	0.0128 (7)	0.0021 (6)	−0.0004 (6)	−0.0034 (6)
C5	0.0180 (8)	0.0172 (8)	0.0177 (8)	−0.0014 (6)	−0.0022 (6)	−0.0043 (6)
C6	0.0157 (8)	0.0225 (8)	0.0144 (8)	0.0045 (7)	−0.0029 (6)	−0.0021 (6)
C7	0.0125 (7)	0.0185 (8)	0.0150 (8)	0.0015 (6)	−0.0024 (6)	−0.0025 (6)
C8	0.0137 (7)	0.0185 (7)	0.0202 (8)	−0.0026 (6)	−0.0021 (6)	−0.0018 (6)
C9	0.0169 (7)	0.0129 (7)	0.0196 (8)	−0.0008 (6)	0.0022 (6)	0.0011 (6)
C10	0.0157 (7)	0.0106 (7)	0.0149 (7)	0.0023 (6)	0.0015 (6)	0.0004 (6)
C11	0.0139 (7)	0.0139 (8)	0.0137 (7)	0.0019 (6)	0.0041 (6)	−0.0023 (6)
C12	0.0134 (7)	0.0168 (7)	0.0187 (8)	0.0007 (6)	−0.0017 (7)	0.0000 (6)
C13	0.0207 (9)	0.0222 (8)	0.0292 (9)	0.0024 (7)	−0.0007 (7)	−0.0052 (7)
C14	0.0209 (8)	0.0245 (9)	0.0270 (9)	0.0008 (7)	−0.0075 (7)	0.0012 (7)
C15	0.0224 (8)	0.0230 (8)	0.0237 (8)	−0.0003 (8)	−0.0005 (7)	0.0029 (7)

Geometric parameters (Å, º)

Cl1—C1	1.7411 (14)	C6—H6	0.9500
O1—C7	1.3744 (15)	C7—C8	1.360 (2)
O1—C10	1.3795 (16)	C8—C9	1.4252 (19)
O2—C11	1.2398 (15)	C8—H8	0.9500
N1—C11	1.3465 (17)	C9—C10	1.3561 (18)
N1—N2	1.4174 (16)	C9—H9	0.9500
N1—H1A	0.882 (15)	C10—C11	1.4771 (19)
N2—C12	1.4999 (18)	C12—C14	1.5289 (19)
N2—H2A	0.922 (13)	C12—C13	1.5296 (18)
C1—C2	1.3866 (19)	C12—C15	1.5311 (18)
C1—C6	1.3889 (19)	C13—H13A	0.9800
C2—C3	1.3861 (17)	C13—H13B	0.9800
C2—H2	0.9500	C13—H13C	0.9800
C3—C4	1.4029 (19)	C14—H14A	0.9800
C3—H3	0.9500	C14—H14B	0.9800
C4—C5	1.4009 (18)	C14—H14C	0.9800
C4—C7	1.4578 (19)	C15—H15A	0.9800
C5—C6	1.3906 (19)	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C7—O1—C10	106.97 (10)	C10—C9—H9	126.8
C11—N1—N2	121.66 (12)	C8—C9—H9	126.8
C11—N1—H1A	119.9 (10)	C9—C10—O1	109.95 (12)
N2—N1—H1A	114.2 (10)	C9—C10—C11	133.51 (13)
N1—N2—C12	112.24 (10)	O1—C10—C11	116.41 (12)
N1—N2—H2A	106.0 (9)	O2—C11—N1	123.82 (13)
C12—N2—H2A	106.6 (9)	O2—C11—C10	121.41 (13)
C2—C1—C6	121.36 (13)	N1—C11—C10	114.74 (12)
C2—C1—Cl1	119.06 (11)	N2—C12—C14	104.77 (11)
C6—C1—Cl1	119.58 (11)	N2—C12—C13	112.52 (12)
C3—C2—C1	119.11 (13)	C14—C12—C13	109.88 (12)
C3—C2—H2	120.4	N2—C12—C15	108.52 (11)
C1—C2—H2	120.4	C14—C12—C15	110.58 (12)
C2—C3—C4	120.97 (14)	C13—C12—C15	110.44 (12)
C2—C3—H3	119.5	C12—C13—H13A	109.5
C4—C3—H3	119.5	C12—C13—H13B	109.5
C5—C4—C3	118.69 (13)	H13A—C13—H13B	109.5
C5—C4—C7	121.77 (13)	C12—C13—H13C	109.5
C3—C4—C7	119.54 (13)	H13A—C13—H13C	109.5
C6—C5—C4	120.66 (13)	H13B—C13—H13C	109.5
C6—C5—H5	119.7	C12—C14—H14A	109.5
C4—C5—H5	119.7	C12—C14—H14B	109.5
C1—C6—C5	119.20 (13)	H14A—C14—H14B	109.5
C1—C6—H6	120.4	C12—C14—H14C	109.5
C5—C6—H6	120.4	H14A—C14—H14C	109.5
C8—C7—O1	109.33 (12)	H14B—C14—H14C	109.5
C8—C7—C4	136.18 (13)	C12—C15—H15A	109.5
O1—C7—C4	114.49 (12)	C12—C15—H15B	109.5
C7—C8—C9	107.33 (13)	H15A—C15—H15B	109.5
C7—C8—H8	126.3	C12—C15—H15C	109.5
C9—C8—H8	126.3	H15A—C15—H15C	109.5
C10—C9—C8	106.41 (13)	H15B—C15—H15C	109.5
C11—N1—N2—C12	−101.13 (14)	O1—C7—C8—C9	−0.05 (16)
C6—C1—C2—C3	0.5 (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—C4	0.0 (2)	C8—C9—C10—O1	0.73 (16)
C2—C3—C4—C5	−0.3 (2)	C8—C9—C10—C11	176.25 (14)
C2—C3—C4—C7	179.88 (13)	C7—O1—C10—C9	−0.77 (15)
C3—C4—C5—C6	0.2 (2)	C7—O1—C10—C11	−177.14 (11)
C7—C4—C5—C6	180.00 (13)	N2—N1—C11—O2	5.2 (2)
C2—C1—C6—C5	−0.6 (2)	N2—N1—C11—C10	−176.72 (11)
Cl1—C1—C6—C5	179.45 (10)	C9—C10—C11—O2	1.9 (2)
C4—C5—C6—C1	0.3 (2)	O1—C10—C11—O2	177.18 (12)
C10—O1—C7—C8	0.49 (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—C8	164.26 (16)	N1—N2—C12—C13	64.11 (15)
C5—C4—C7—O1	165.04 (12)	N1—N2—C12—C15	−58.41 (14)
C3—C4—C7—O1	−15.13 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.882 (15)	2.026 (16)	2.8744 (15)	160.9 (14)

Symmetry code: (i) −x+2, y−1/2, −z+3/2.