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The title compound, C10H14N2O2, is an important inter­mediate for the synthesis of biologically active heterocyclic compounds. The planar hydrazide group is oriented with respect to the benzene ring at a dihedral angle of 81.27 (3)°. The crystal structure is stabilized by N—H...O and N—H...N hydrogen bonding.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025810/xu2262sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025810/xu2262Isup2.hkl
Contains datablock I

CCDC reference: 654850

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.066
  • wR factor = 0.169
  • Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 39 Perc.
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 28.20 From the CIF: _diffrn_reflns_theta_full 28.20 From the CIF: _reflns_number_total 2350 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2492 Completeness (_total/calc) 94.30% RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.126 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.13 PLAT230_ALERT_2_C Hirshfeld Test Diff for C2 - C3 .. 5.21 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 3.14 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-marcapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound and reported its crystal structure.

The molecular structure of (I) is shown in Fig. 1. Bond distances and angles are within expected ranges. The dihedral angle between the planar hydrazidic group (C9/O1/N1/N2) and the benzene ring (C1—C6) is 81.27 (3)°. The crystal structure is stabilized by N–H···O and N–H···N hydrogen bonding (Fig. 2).

Related literature top

For general background, see: Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Ahmad et al. (2001); Al-Soud et al. (2004); El-Emam et al. (2004). For synthesis, see: Furniss et al. (1978).

Experimental top

The title compound is synthesized by the reaction of methyl ester of 3-(4-trimethoxyphenyl)propanoic aicd with hyrazine hydrate using the reported procedure (Furniss et al., 1978). A mixture of methyl-3-(4-trimethoxyphenyl)propanoate (2.08 g, 10 mmol) and hydrazine hydrate (15 ml, 80%) in absolute ethanol (50 ml) was refluxed for 5 h at 413–423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol solution to give the title compound (yield: 1.80 g, 87%). Colorless single crystals were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement top

Amino H atoms were located in a difference Fourier map and refined isotropically. Other H atoms were placed in calculated positions with N—H = 0.88 Å and C—H = 0.95 (aromatic), 0.99 (methylene) or 0.98 Å (methyl), and refined in riding mode with Uiso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C,N) for others.

Structure description top

Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-marcapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound and reported its crystal structure.

The molecular structure of (I) is shown in Fig. 1. Bond distances and angles are within expected ranges. The dihedral angle between the planar hydrazidic group (C9/O1/N1/N2) and the benzene ring (C1—C6) is 81.27 (3)°. The crystal structure is stabilized by N–H···O and N–H···N hydrogen bonding (Fig. 2).

For general background, see: Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Ahmad et al. (2001); Al-Soud et al. (2004); El-Emam et al. (2004). For synthesis, see: Furniss et al. (1978).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids (arbitrary spheres for H atoms).
[Figure 2] Fig. 2. Crystal packing of (I). Dashed lines indicate hydrogen bonds.
[Figure 3] Fig. 3. The synthetic route for the formation of the title compound.
3-(4-Methoxyphenyl)propanohydrazide top
Crystal data top
C10H14N2O2F(000) = 416
Mr = 194.23Dx = 1.276 Mg m3
Dm = 1.253 Mg m3
Dm measured by not measured
Monoclinic, P21/cMelting point: 383(2) K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 18.519 (9) ÅCell parameters from 691 reflections
b = 4.816 (2) Åθ = 3.4–23.6°
c = 11.884 (6) ŵ = 0.09 mm1
β = 107.521 (7)°T = 100 K
V = 1010.7 (8) Å3Block, colorless
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
910 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.126
Graphite monochromatorθmax = 28.2°, θmin = 2.3°
φ and ω scansh = 2424
7527 measured reflectionsk = 66
2350 independent reflectionsl = 1515
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)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 0.83 w = 1/[σ2(Fo2) + (0.0666P)2]
where P = (Fo2 + 2Fc2)/3
2350 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C10H14N2O2V = 1010.7 (8) Å3
Mr = 194.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 18.519 (9) ŵ = 0.09 mm1
b = 4.816 (2) ÅT = 100 K
c = 11.884 (6) Å0.30 × 0.20 × 0.10 mm
β = 107.521 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
910 reflections with I > 2σ(I)
7527 measured reflectionsRint = 0.126
2350 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 0.83Δρmax = 0.18 e Å3
2350 reflectionsΔρmin = 0.28 e Å3
136 parameters
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
C10.74807 (18)0.8352 (6)0.4237 (3)0.0471 (10)
C20.7369 (2)1.0414 (7)0.3383 (3)0.0582 (12)
H20.68691.10330.29980.070*
C30.7965 (2)1.1595 (6)0.3074 (3)0.0500 (10)
H30.78681.29860.24800.060*
C40.86920 (19)1.0760 (6)0.3622 (3)0.0423 (9)
C50.88298 (19)0.8717 (6)0.4493 (3)0.0443 (9)
H50.93330.81260.48810.053*
C60.82279 (19)0.7562 (6)0.4786 (3)0.0453 (9)
H60.83270.61800.53840.054*
C70.6831 (2)0.7041 (8)0.4551 (4)0.0615 (12)
H7A0.69300.50290.46820.074*
H7B0.63640.72570.38800.074*
C80.6703 (2)0.8297 (7)0.5645 (3)0.0487 (10)
H8A0.71650.80330.63220.058*
H8B0.66181.03190.55230.058*
C90.6042 (2)0.7035 (6)0.5935 (3)0.0453 (9)
C100.9193 (3)1.3676 (7)0.2403 (4)0.0759 (14)
H10A0.88851.27780.16770.114*
H10B0.96801.42440.23070.114*
H10C0.89261.53150.25640.114*
N10.56013 (17)0.8802 (5)0.6305 (2)0.0478 (8)
H10.57211.05760.63620.057*
N20.4950 (2)0.7934 (6)0.6610 (3)0.0473 (9)
O10.59112 (13)0.4495 (4)0.58570 (18)0.0472 (7)
O20.93238 (14)1.1750 (5)0.3375 (2)0.0552 (7)
H2A0.5135 (17)0.657 (7)0.712 (3)0.044 (10)*
H2B0.4597 (19)0.728 (7)0.599 (3)0.050 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.035 (2)0.0251 (17)0.069 (3)0.0069 (15)0.0031 (18)0.0161 (17)
C20.045 (2)0.0343 (19)0.068 (3)0.0054 (18)0.0237 (19)0.0168 (19)
C30.058 (2)0.0218 (16)0.048 (2)0.0020 (16)0.0172 (19)0.0007 (15)
C40.046 (2)0.0263 (17)0.044 (2)0.0077 (15)0.0021 (17)0.0046 (15)
C50.042 (2)0.0303 (18)0.049 (2)0.0050 (16)0.0027 (17)0.0021 (15)
C60.046 (2)0.0245 (16)0.058 (2)0.0002 (15)0.0055 (18)0.0052 (15)
C70.048 (2)0.053 (2)0.079 (3)0.0165 (19)0.012 (2)0.030 (2)
C80.064 (2)0.0272 (17)0.041 (2)0.0156 (17)0.0050 (18)0.0060 (15)
C90.068 (3)0.0252 (16)0.0290 (18)0.0131 (17)0.0067 (17)0.0032 (15)
C100.133 (4)0.030 (2)0.067 (3)0.020 (2)0.033 (3)0.0015 (19)
N10.081 (2)0.0240 (14)0.0324 (16)0.0170 (15)0.0088 (16)0.0044 (11)
N20.084 (3)0.0275 (16)0.0252 (17)0.0105 (16)0.0086 (18)0.0009 (13)
O10.0653 (16)0.0243 (11)0.0417 (13)0.0135 (11)0.0006 (12)0.0036 (10)
O20.0625 (17)0.0445 (15)0.0554 (16)0.0158 (13)0.0129 (13)0.0019 (12)
Geometric parameters (Å, º) top
C1—C21.390 (5)C7—H7B0.9900
C1—C61.393 (4)C8—C91.498 (5)
C1—C71.502 (5)C8—H8A0.9900
C2—C31.385 (5)C8—H8B0.9900
C2—H20.9500C9—O11.245 (3)
C3—C41.368 (4)C9—N11.341 (4)
C3—H30.9500C10—O21.445 (4)
C4—O21.374 (4)C10—H10A0.9800
C4—C51.395 (4)C10—H10B0.9800
C5—C61.381 (4)C10—H10C0.9800
C5—H50.9500N1—N21.423 (4)
C6—H60.9500N1—H10.8800
C7—C81.515 (5)N2—H2A0.89 (3)
C7—H7A0.9900N2—H2B0.88 (3)
C2—C1—C6116.4 (3)H7A—C7—H7B107.8
C2—C1—C7121.9 (3)C9—C8—C7112.6 (3)
C6—C1—C7121.7 (3)C9—C8—H8A109.1
C3—C2—C1122.1 (3)C7—C8—H8A109.1
C3—C2—H2118.9C9—C8—H8B109.1
C1—C2—H2118.9C7—C8—H8B109.1
C4—C3—C2120.1 (3)H8A—C8—H8B107.8
C4—C3—H3120.0O1—C9—N1121.6 (3)
C2—C3—H3120.0O1—C9—C8122.4 (3)
C3—C4—O2125.1 (3)N1—C9—C8116.0 (3)
C3—C4—C5119.7 (3)O2—C10—H10A109.5
O2—C4—C5115.2 (3)O2—C10—H10B109.5
C6—C5—C4119.4 (3)H10A—C10—H10B109.5
C6—C5—H5120.3O2—C10—H10C109.5
C4—C5—H5120.3H10A—C10—H10C109.5
C5—C6—C1122.3 (3)H10B—C10—H10C109.5
C5—C6—H6118.8C9—N1—N2122.9 (3)
C1—C6—H6118.8C9—N1—H1118.6
C1—C7—C8112.9 (3)N2—N1—H1118.6
C1—C7—H7A109.0N1—N2—H2A102 (2)
C8—C7—H7A109.0N1—N2—H2B111 (2)
C1—C7—H7B109.0H2A—N2—H2B110 (3)
C8—C7—H7B109.0C4—O2—C10116.5 (3)
C6—C1—C2—C31.2 (5)C2—C1—C7—C898.0 (4)
C7—C1—C2—C3178.8 (3)C6—C1—C7—C882.1 (4)
C1—C2—C3—C40.7 (5)C1—C7—C8—C9178.4 (3)
C2—C3—C4—O2178.9 (3)C7—C8—C9—O141.3 (5)
C2—C3—C4—C50.0 (5)C7—C8—C9—N1139.8 (3)
C3—C4—C5—C60.2 (5)O1—C9—N1—N21.4 (5)
O2—C4—C5—C6178.9 (3)C8—C9—N1—N2179.7 (3)
C4—C5—C6—C10.4 (5)C3—C4—O2—C104.6 (5)
C2—C1—C6—C51.0 (5)C5—C4—O2—C10174.4 (3)
C7—C1—C6—C5179.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.042.883 (3)159
N2—H2A···N2ii0.89 (3)2.35 (4)3.174 (4)154 (3)
N2—H2B···O1iii0.88 (3)2.28 (4)3.112 (4)158 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC10H14N2O2
Mr194.23
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)18.519 (9), 4.816 (2), 11.884 (6)
β (°) 107.521 (7)
V3)1010.7 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7527, 2350, 910
Rint0.126
(sin θ/λ)max1)0.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.169, 0.83
No. of reflections2350
No. of parameters136
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.28

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.042.883 (3)159
N2—H2A···N2ii0.89 (3)2.35 (4)3.174 (4)154 (3)
N2—H2B···O1iii0.88 (3)2.28 (4)3.112 (4)158 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1.
 

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