Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025810/xu2262sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025810/xu2262Isup2.hkl |
CCDC reference: 654850
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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).
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.
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.
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).
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.
C10H14N2O2 | F(000) = 416 |
Mr = 194.23 | Dx = 1.276 Mg m−3 Dm = 1.253 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Melting point: 383(2) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 18.519 (9) Å | Cell parameters from 691 reflections |
b = 4.816 (2) Å | θ = 3.4–23.6° |
c = 11.884 (6) Å | µ = 0.09 mm−1 |
β = 107.521 (7)° | T = 100 K |
V = 1010.7 (8) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 910 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.126 |
Graphite monochromator | θmax = 28.2°, θmin = 2.3° |
φ and ω scans | h = −24→24 |
7527 measured reflections | k = −6→6 |
2350 independent reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H 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 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C10H14N2O2 | V = 1010.7 (8) Å3 |
Mr = 194.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.519 (9) Å | µ = 0.09 mm−1 |
b = 4.816 (2) Å | T = 100 K |
c = 11.884 (6) Å | 0.30 × 0.20 × 0.10 mm |
β = 107.521 (7)° |
Bruker SMART CCD area-detector diffractometer | 910 reflections with I > 2σ(I) |
7527 measured reflections | Rint = 0.126 |
2350 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.169 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.83 | Δρmax = 0.18 e Å−3 |
2350 reflections | Δρmin = −0.28 e Å−3 |
136 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.74807 (18) | 0.8352 (6) | 0.4237 (3) | 0.0471 (10) | |
C2 | 0.7369 (2) | 1.0414 (7) | 0.3383 (3) | 0.0582 (12) | |
H2 | 0.6869 | 1.1033 | 0.2998 | 0.070* | |
C3 | 0.7965 (2) | 1.1595 (6) | 0.3074 (3) | 0.0500 (10) | |
H3 | 0.7868 | 1.2986 | 0.2480 | 0.060* | |
C4 | 0.86920 (19) | 1.0760 (6) | 0.3622 (3) | 0.0423 (9) | |
C5 | 0.88298 (19) | 0.8717 (6) | 0.4493 (3) | 0.0443 (9) | |
H5 | 0.9333 | 0.8126 | 0.4881 | 0.053* | |
C6 | 0.82279 (19) | 0.7562 (6) | 0.4786 (3) | 0.0453 (9) | |
H6 | 0.8327 | 0.6180 | 0.5384 | 0.054* | |
C7 | 0.6831 (2) | 0.7041 (8) | 0.4551 (4) | 0.0615 (12) | |
H7A | 0.6930 | 0.5029 | 0.4682 | 0.074* | |
H7B | 0.6364 | 0.7257 | 0.3880 | 0.074* | |
C8 | 0.6703 (2) | 0.8297 (7) | 0.5645 (3) | 0.0487 (10) | |
H8A | 0.7165 | 0.8033 | 0.6322 | 0.058* | |
H8B | 0.6618 | 1.0319 | 0.5523 | 0.058* | |
C9 | 0.6042 (2) | 0.7035 (6) | 0.5935 (3) | 0.0453 (9) | |
C10 | 0.9193 (3) | 1.3676 (7) | 0.2403 (4) | 0.0759 (14) | |
H10A | 0.8885 | 1.2778 | 0.1677 | 0.114* | |
H10B | 0.9680 | 1.4244 | 0.2307 | 0.114* | |
H10C | 0.8926 | 1.5315 | 0.2564 | 0.114* | |
N1 | 0.56013 (17) | 0.8802 (5) | 0.6305 (2) | 0.0478 (8) | |
H1 | 0.5721 | 1.0576 | 0.6362 | 0.057* | |
N2 | 0.4950 (2) | 0.7934 (6) | 0.6610 (3) | 0.0473 (9) | |
O1 | 0.59112 (13) | 0.4495 (4) | 0.58570 (18) | 0.0472 (7) | |
O2 | 0.93238 (14) | 1.1750 (5) | 0.3375 (2) | 0.0552 (7) | |
H2A | 0.5135 (17) | 0.657 (7) | 0.712 (3) | 0.044 (10)* | |
H2B | 0.4597 (19) | 0.728 (7) | 0.599 (3) | 0.050 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.035 (2) | 0.0251 (17) | 0.069 (3) | −0.0069 (15) | −0.0031 (18) | −0.0161 (17) |
C2 | 0.045 (2) | 0.0343 (19) | 0.068 (3) | 0.0054 (18) | −0.0237 (19) | −0.0168 (19) |
C3 | 0.058 (2) | 0.0218 (16) | 0.048 (2) | −0.0020 (16) | −0.0172 (19) | −0.0007 (15) |
C4 | 0.046 (2) | 0.0263 (17) | 0.044 (2) | −0.0077 (15) | −0.0021 (17) | −0.0046 (15) |
C5 | 0.042 (2) | 0.0303 (18) | 0.049 (2) | 0.0050 (16) | −0.0027 (17) | 0.0021 (15) |
C6 | 0.046 (2) | 0.0245 (16) | 0.058 (2) | −0.0002 (15) | 0.0055 (18) | 0.0052 (15) |
C7 | 0.048 (2) | 0.053 (2) | 0.079 (3) | −0.0165 (19) | 0.012 (2) | −0.030 (2) |
C8 | 0.064 (2) | 0.0272 (17) | 0.041 (2) | −0.0156 (17) | −0.0050 (18) | −0.0060 (15) |
C9 | 0.068 (3) | 0.0252 (16) | 0.0290 (18) | −0.0131 (17) | −0.0067 (17) | −0.0032 (15) |
C10 | 0.133 (4) | 0.030 (2) | 0.067 (3) | −0.020 (2) | 0.033 (3) | 0.0015 (19) |
N1 | 0.081 (2) | 0.0240 (14) | 0.0324 (16) | −0.0170 (15) | 0.0088 (16) | −0.0044 (11) |
N2 | 0.084 (3) | 0.0275 (16) | 0.0252 (17) | −0.0105 (16) | 0.0086 (18) | 0.0009 (13) |
O1 | 0.0653 (16) | 0.0243 (11) | 0.0417 (13) | −0.0135 (11) | 0.0006 (12) | −0.0036 (10) |
O2 | 0.0625 (17) | 0.0445 (15) | 0.0554 (16) | −0.0158 (13) | 0.0129 (13) | 0.0019 (12) |
C1—C2 | 1.390 (5) | C7—H7B | 0.9900 |
C1—C6 | 1.393 (4) | C8—C9 | 1.498 (5) |
C1—C7 | 1.502 (5) | C8—H8A | 0.9900 |
C2—C3 | 1.385 (5) | C8—H8B | 0.9900 |
C2—H2 | 0.9500 | C9—O1 | 1.245 (3) |
C3—C4 | 1.368 (4) | C9—N1 | 1.341 (4) |
C3—H3 | 0.9500 | C10—O2 | 1.445 (4) |
C4—O2 | 1.374 (4) | C10—H10A | 0.9800 |
C4—C5 | 1.395 (4) | C10—H10B | 0.9800 |
C5—C6 | 1.381 (4) | C10—H10C | 0.9800 |
C5—H5 | 0.9500 | N1—N2 | 1.423 (4) |
C6—H6 | 0.9500 | N1—H1 | 0.8800 |
C7—C8 | 1.515 (5) | N2—H2A | 0.89 (3) |
C7—H7A | 0.9900 | N2—H2B | 0.88 (3) |
C2—C1—C6 | 116.4 (3) | H7A—C7—H7B | 107.8 |
C2—C1—C7 | 121.9 (3) | C9—C8—C7 | 112.6 (3) |
C6—C1—C7 | 121.7 (3) | C9—C8—H8A | 109.1 |
C3—C2—C1 | 122.1 (3) | C7—C8—H8A | 109.1 |
C3—C2—H2 | 118.9 | C9—C8—H8B | 109.1 |
C1—C2—H2 | 118.9 | C7—C8—H8B | 109.1 |
C4—C3—C2 | 120.1 (3) | H8A—C8—H8B | 107.8 |
C4—C3—H3 | 120.0 | O1—C9—N1 | 121.6 (3) |
C2—C3—H3 | 120.0 | O1—C9—C8 | 122.4 (3) |
C3—C4—O2 | 125.1 (3) | N1—C9—C8 | 116.0 (3) |
C3—C4—C5 | 119.7 (3) | O2—C10—H10A | 109.5 |
O2—C4—C5 | 115.2 (3) | O2—C10—H10B | 109.5 |
C6—C5—C4 | 119.4 (3) | H10A—C10—H10B | 109.5 |
C6—C5—H5 | 120.3 | O2—C10—H10C | 109.5 |
C4—C5—H5 | 120.3 | H10A—C10—H10C | 109.5 |
C5—C6—C1 | 122.3 (3) | H10B—C10—H10C | 109.5 |
C5—C6—H6 | 118.8 | C9—N1—N2 | 122.9 (3) |
C1—C6—H6 | 118.8 | C9—N1—H1 | 118.6 |
C1—C7—C8 | 112.9 (3) | N2—N1—H1 | 118.6 |
C1—C7—H7A | 109.0 | N1—N2—H2A | 102 (2) |
C8—C7—H7A | 109.0 | N1—N2—H2B | 111 (2) |
C1—C7—H7B | 109.0 | H2A—N2—H2B | 110 (3) |
C8—C7—H7B | 109.0 | C4—O2—C10 | 116.5 (3) |
C6—C1—C2—C3 | 1.2 (5) | C2—C1—C7—C8 | −98.0 (4) |
C7—C1—C2—C3 | −178.8 (3) | C6—C1—C7—C8 | 82.1 (4) |
C1—C2—C3—C4 | −0.7 (5) | C1—C7—C8—C9 | 178.4 (3) |
C2—C3—C4—O2 | 178.9 (3) | C7—C8—C9—O1 | 41.3 (5) |
C2—C3—C4—C5 | 0.0 (5) | C7—C8—C9—N1 | −139.8 (3) |
C3—C4—C5—C6 | 0.2 (5) | O1—C9—N1—N2 | −1.4 (5) |
O2—C4—C5—C6 | −178.9 (3) | C8—C9—N1—N2 | 179.7 (3) |
C4—C5—C6—C1 | 0.4 (5) | C3—C4—O2—C10 | −4.6 (5) |
C2—C1—C6—C5 | −1.0 (5) | C5—C4—O2—C10 | 174.4 (3) |
C7—C1—C6—C5 | 179.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 2.04 | 2.883 (3) | 159 |
N2—H2A···N2ii | 0.89 (3) | 2.35 (4) | 3.174 (4) | 154 (3) |
N2—H2B···O1iii | 0.88 (3) | 2.28 (4) | 3.112 (4) | 158 (3) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H14N2O2 |
Mr | 194.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 18.519 (9), 4.816 (2), 11.884 (6) |
β (°) | 107.521 (7) |
V (Å3) | 1010.7 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7527, 2350, 910 |
Rint | 0.126 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.169, 0.83 |
No. of reflections | 2350 |
No. of parameters | 136 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.28 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 2.04 | 2.883 (3) | 159 |
N2—H2A···N2ii | 0.89 (3) | 2.35 (4) | 3.174 (4) | 154 (3) |
N2—H2B···O1iii | 0.88 (3) | 2.28 (4) | 3.112 (4) | 158 (3) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1. |
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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).