Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025147/hk2255sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025147/hk2255Isup2.hkl |
CCDC reference: 651518
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.043
- wR factor = 0.077
- Data-to-parameter ratio = 17.0
checkCIF/PLATON results
No syntax errors found
Alert level C GOODF01_ALERT_2_C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 0.783 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C9 .. 5.92 su PLAT353_ALERT_3_C Long N-H Bond (0.87A) N2 - H2B ... 1.02 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. O3 .. 2.62 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound, (I), is synthesized by the reaction of methyl ester of 3-(3,4,5-trimethoxyphenyl)propanoic acid with hdyrazine hydrate using the reported procedure (Furniss et al., 1978). For the preparation of (I), a mixture of methyl-3-(3,4,5-trimethoxyphenyl)propanoate (2.68 g, 10 mmol) and hydrazine hydrate (80%, 15 ml) 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 (30%) to give the title compound (yield: 1.45 g, 91%, m.p. 398–399 K). Colourless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.
H atoms of NH2 groups were located in difference syntheses and refined isotropically [N—H = 0.883 (17)–1.016 (19) Å and Uiso(H) = 0.027 (6)–0.046 (6) Å2]. The remaining H atoms were positioned geometrically, with N—H = 0.88 Å (for NH) and C—H = 0.95, 0.99 and 0.98 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
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-mercapto-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, (I), and reported its crystal structure.
The asymmetric unit of the title compound, (I), contains two molecules (Fig. 1), in which the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar hydrazidic groups A (C9/O1/N1/N2), C (C21/O5/N3/N4) and benzene rings B (C1—C6), D (C13—C18) are A/B = 65.86 (2)° and C/D = 51.16 (2)°.
In the crystal structure, the intra- and intermolecular N—H···O hydrogen bonds link the molecules to form a supramolecular structure (Fig. 2).
For general backgroud, 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); Allen et al. (1987); Furniss et al. (1978).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
C12H18N2O4 | F(000) = 1088 |
Mr = 254.28 | Dx = 1.364 Mg m−3 Dm = 1.323 Mg m−3 Dm measured by not measured |
Monoclinic, P21/n | Melting point: 398(1) K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7770 (14) Å | Cell parameters from 2527 reflections |
b = 20.189 (3) Å | θ = 2.4–24.6° |
c = 12.7300 (19) Å | µ = 0.10 mm−1 |
β = 99.618 (3)° | T = 100 K |
V = 2477.4 (6) Å3 | Plate, colourless |
Z = 8 | 0.20 × 0.20 × 0.05 mm |
Bruker APEXII diffractometer | 5897 independent reflections |
Radiation source: fine-focus sealed tube | 3183 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
φ and ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.980, Tmax = 0.995 | k = −26→26 |
21411 measured reflections | l = −16→16 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.78 | w = 1/[σ2(Fo2) + (0.0237P)2] where P = (Fo2 + 2Fc2)/3 |
5897 reflections | (Δ/σ)max = 0.001 |
347 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C12H18N2O4 | V = 2477.4 (6) Å3 |
Mr = 254.28 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7770 (14) Å | µ = 0.10 mm−1 |
b = 20.189 (3) Å | T = 100 K |
c = 12.7300 (19) Å | 0.20 × 0.20 × 0.05 mm |
β = 99.618 (3)° |
Bruker APEXII diffractometer | 5897 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3183 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.995 | Rint = 0.066 |
21411 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.78 | Δρmax = 0.34 e Å−3 |
5897 reflections | Δρmin = −0.20 e Å−3 |
347 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 | 0.77225 (17) | 0.10545 (9) | 0.81464 (14) | 0.0210 (4) | |
C2 | 0.82525 (17) | 0.16818 (8) | 0.80155 (14) | 0.0210 (4) | |
H2 | 0.8637 | 0.1779 | 0.7396 | 0.025* | |
C3 | 0.82242 (17) | 0.21655 (8) | 0.87806 (14) | 0.0188 (4) | |
C4 | 0.76614 (17) | 0.20276 (8) | 0.96914 (13) | 0.0186 (4) | |
C5 | 0.71654 (17) | 0.13937 (9) | 0.98398 (13) | 0.0202 (4) | |
C6 | 0.71960 (17) | 0.09074 (8) | 0.90658 (13) | 0.0208 (4) | |
H6 | 0.6856 | 0.0475 | 0.9168 | 0.025* | |
C7 | 0.76846 (19) | 0.05754 (8) | 0.72274 (14) | 0.0254 (5) | |
H7A | 0.7075 | 0.0765 | 0.6600 | 0.031* | |
H7B | 0.8631 | 0.0548 | 0.7050 | 0.031* | |
C8 | 0.71982 (19) | −0.01163 (8) | 0.73887 (14) | 0.0249 (4) | |
H8A | 0.6249 | −0.0106 | 0.7563 | 0.030* | |
H8B | 0.7820 | −0.0329 | 0.7988 | 0.030* | |
C9 | 0.72062 (19) | −0.05062 (8) | 0.63750 (14) | 0.0204 (4) | |
C10 | 0.94256 (18) | 0.29274 (9) | 0.78327 (14) | 0.0262 (5) | |
H10A | 1.0195 | 0.2613 | 0.7860 | 0.039* | |
H10B | 0.9791 | 0.3380 | 0.7891 | 0.039* | |
H10C | 0.8791 | 0.2877 | 0.7155 | 0.039* | |
C11 | 0.63052 (18) | 0.27887 (9) | 1.04707 (14) | 0.0271 (5) | |
H11A | 0.6035 | 0.3061 | 0.9833 | 0.041* | |
H11B | 0.6329 | 0.3064 | 1.1108 | 0.041* | |
H11C | 0.5630 | 0.2430 | 1.0478 | 0.041* | |
C12 | 0.58195 (19) | 0.07283 (8) | 1.08450 (14) | 0.0274 (5) | |
H12A | 0.5059 | 0.0722 | 1.0237 | 0.041* | |
H12B | 0.5437 | 0.0746 | 1.1509 | 0.041* | |
H12C | 0.6380 | 0.0326 | 1.0838 | 0.041* | |
C13 | 0.74678 (17) | 0.22835 (8) | 0.45942 (14) | 0.0182 (4) | |
C14 | 0.80575 (17) | 0.26561 (8) | 0.38682 (13) | 0.0189 (4) | |
H14 | 0.8526 | 0.2441 | 0.3368 | 0.023* | |
C15 | 0.79634 (17) | 0.33430 (8) | 0.38729 (13) | 0.0190 (4) | |
C16 | 0.72976 (18) | 0.36628 (8) | 0.46083 (14) | 0.0201 (4) | |
C17 | 0.66989 (18) | 0.32884 (9) | 0.53305 (14) | 0.0207 (4) | |
C18 | 0.67797 (17) | 0.26049 (8) | 0.53184 (13) | 0.0204 (4) | |
H18 | 0.6361 | 0.2353 | 0.5809 | 0.024* | |
C19 | 0.75655 (18) | 0.15356 (8) | 0.46357 (13) | 0.0210 (4) | |
H19A | 0.6645 | 0.1357 | 0.4713 | 0.025* | |
H19B | 0.8225 | 0.1409 | 0.5282 | 0.025* | |
C20 | 0.80268 (18) | 0.12032 (8) | 0.36739 (13) | 0.0200 (4) | |
H20A | 0.7489 | 0.1387 | 0.3010 | 0.024* | |
H20B | 0.9020 | 0.1299 | 0.3676 | 0.024* | |
C21 | 0.78135 (19) | 0.04633 (8) | 0.36965 (13) | 0.0187 (4) | |
C22 | 0.93915 (17) | 0.34403 (9) | 0.25389 (13) | 0.0234 (4) | |
H22A | 1.0117 | 0.3189 | 0.2995 | 0.035* | |
H22B | 0.9820 | 0.3781 | 0.2152 | 0.035* | |
H22C | 0.8844 | 0.3140 | 0.2029 | 0.035* | |
C23 | 0.60159 (19) | 0.46270 (9) | 0.40771 (14) | 0.0302 (5) | |
H23A | 0.5913 | 0.4502 | 0.3324 | 0.045* | |
H23B | 0.6054 | 0.5111 | 0.4140 | 0.045* | |
H23C | 0.5223 | 0.4460 | 0.4377 | 0.045* | |
C24 | 0.54841 (19) | 0.33045 (9) | 0.68159 (14) | 0.0295 (5) | |
H24A | 0.4746 | 0.3011 | 0.6470 | 0.044* | |
H24B | 0.5098 | 0.3622 | 0.7270 | 0.044* | |
H24C | 0.6207 | 0.3041 | 0.7253 | 0.044* | |
N1 | 0.59562 (14) | −0.06535 (6) | 0.58244 (11) | 0.0192 (3) | |
H1 | 0.5218 | −0.0535 | 0.6091 | 0.023* | |
N2 | 0.57586 (16) | −0.09888 (8) | 0.48405 (12) | 0.0211 (4) | |
N3 | 0.89550 (15) | 0.00953 (7) | 0.37315 (11) | 0.0215 (4) | |
H3 | 0.9754 | 0.0296 | 0.3730 | 0.026* | |
N4 | 0.89270 (16) | −0.06062 (7) | 0.37717 (14) | 0.0240 (4) | |
O1 | 0.83011 (12) | −0.06662 (6) | 0.60651 (9) | 0.0227 (3) | |
O2 | 0.86955 (12) | 0.27991 (6) | 0.86969 (9) | 0.0239 (3) | |
O3 | 0.76544 (12) | 0.25113 (5) | 1.04613 (9) | 0.0218 (3) | |
O4 | 0.66724 (12) | 0.12996 (6) | 1.07742 (9) | 0.0252 (3) | |
O5 | 0.66524 (12) | 0.02119 (5) | 0.36754 (9) | 0.0235 (3) | |
O6 | 0.85059 (12) | 0.37485 (6) | 0.31826 (9) | 0.0242 (3) | |
O7 | 0.72754 (12) | 0.43463 (6) | 0.46494 (9) | 0.0248 (3) | |
O8 | 0.60708 (13) | 0.36544 (6) | 0.60212 (9) | 0.0286 (3) | |
H4A | 0.8601 (19) | −0.0726 (9) | 0.4448 (15) | 0.046 (6)* | |
H2A | 0.6186 (17) | −0.1373 (8) | 0.4963 (13) | 0.027 (6)* | |
H2B | 0.6228 (19) | −0.0706 (9) | 0.4344 (15) | 0.046 (6)* | |
H4B | 0.8200 (19) | −0.0721 (8) | 0.3242 (14) | 0.035 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0170 (10) | 0.0238 (11) | 0.0220 (10) | 0.0032 (8) | 0.0025 (8) | −0.0044 (8) |
C2 | 0.0186 (10) | 0.0257 (11) | 0.0192 (10) | −0.0011 (8) | 0.0047 (8) | −0.0024 (8) |
C3 | 0.0158 (10) | 0.0163 (10) | 0.0224 (11) | 0.0018 (8) | −0.0023 (8) | −0.0016 (8) |
C4 | 0.0171 (10) | 0.0186 (10) | 0.0184 (10) | 0.0023 (8) | −0.0020 (8) | −0.0047 (8) |
C5 | 0.0189 (10) | 0.0258 (11) | 0.0144 (10) | 0.0046 (8) | −0.0014 (8) | 0.0000 (8) |
C6 | 0.0193 (10) | 0.0172 (10) | 0.0246 (11) | −0.0003 (8) | −0.0002 (8) | −0.0017 (8) |
C7 | 0.0286 (11) | 0.0236 (11) | 0.0259 (11) | −0.0005 (9) | 0.0096 (9) | −0.0038 (9) |
C8 | 0.0272 (11) | 0.0257 (11) | 0.0230 (11) | −0.0016 (9) | 0.0078 (9) | −0.0044 (9) |
C9 | 0.0219 (11) | 0.0183 (10) | 0.0216 (10) | −0.0042 (8) | 0.0050 (8) | 0.0005 (8) |
C10 | 0.0223 (11) | 0.0287 (11) | 0.0286 (11) | −0.0058 (9) | 0.0070 (9) | −0.0036 (9) |
C11 | 0.0250 (11) | 0.0239 (11) | 0.0329 (12) | 0.0040 (9) | 0.0060 (9) | −0.0057 (9) |
C12 | 0.0305 (11) | 0.0269 (11) | 0.0266 (11) | 0.0003 (9) | 0.0101 (9) | −0.0001 (9) |
C13 | 0.0172 (10) | 0.0185 (10) | 0.0183 (10) | −0.0036 (8) | 0.0010 (8) | −0.0009 (8) |
C14 | 0.0192 (10) | 0.0202 (10) | 0.0181 (10) | −0.0010 (8) | 0.0052 (8) | −0.0026 (8) |
C15 | 0.0172 (10) | 0.0214 (10) | 0.0182 (10) | −0.0044 (8) | 0.0030 (8) | 0.0025 (8) |
C16 | 0.0203 (10) | 0.0155 (10) | 0.0237 (10) | −0.0038 (8) | 0.0017 (8) | −0.0034 (8) |
C17 | 0.0189 (10) | 0.0254 (11) | 0.0182 (10) | −0.0036 (8) | 0.0045 (8) | −0.0066 (8) |
C18 | 0.0208 (10) | 0.0242 (11) | 0.0166 (10) | −0.0072 (8) | 0.0043 (8) | 0.0015 (8) |
C19 | 0.0222 (11) | 0.0212 (10) | 0.0210 (10) | −0.0030 (8) | 0.0077 (8) | 0.0008 (8) |
C20 | 0.0178 (10) | 0.0214 (10) | 0.0219 (10) | −0.0009 (8) | 0.0065 (8) | 0.0010 (8) |
C21 | 0.0202 (10) | 0.0219 (10) | 0.0152 (10) | 0.0001 (8) | 0.0067 (8) | −0.0003 (8) |
C22 | 0.0234 (11) | 0.0287 (11) | 0.0188 (10) | −0.0045 (9) | 0.0057 (8) | 0.0001 (8) |
C23 | 0.0323 (12) | 0.0277 (11) | 0.0306 (12) | 0.0048 (9) | 0.0053 (9) | −0.0032 (9) |
C24 | 0.0315 (12) | 0.0368 (12) | 0.0232 (11) | −0.0061 (10) | 0.0134 (9) | −0.0072 (9) |
N1 | 0.0179 (8) | 0.0204 (8) | 0.0203 (8) | −0.0012 (7) | 0.0064 (7) | −0.0063 (7) |
N2 | 0.0246 (9) | 0.0208 (9) | 0.0179 (9) | 0.0003 (8) | 0.0031 (7) | −0.0032 (7) |
N3 | 0.0185 (9) | 0.0173 (8) | 0.0300 (9) | −0.0042 (7) | 0.0082 (7) | −0.0004 (7) |
N4 | 0.0263 (10) | 0.0181 (9) | 0.0286 (10) | −0.0007 (8) | 0.0073 (8) | 0.0005 (8) |
O1 | 0.0165 (7) | 0.0282 (7) | 0.0245 (7) | −0.0012 (6) | 0.0065 (6) | −0.0037 (6) |
O2 | 0.0252 (7) | 0.0215 (7) | 0.0256 (8) | −0.0040 (6) | 0.0063 (6) | −0.0035 (6) |
O3 | 0.0201 (7) | 0.0221 (7) | 0.0222 (7) | 0.0017 (6) | 0.0003 (5) | −0.0083 (6) |
O4 | 0.0339 (8) | 0.0224 (7) | 0.0197 (7) | −0.0045 (6) | 0.0061 (6) | −0.0026 (6) |
O5 | 0.0179 (7) | 0.0218 (7) | 0.0323 (8) | −0.0028 (6) | 0.0084 (6) | −0.0003 (6) |
O6 | 0.0271 (8) | 0.0218 (7) | 0.0265 (8) | −0.0011 (6) | 0.0130 (6) | 0.0038 (6) |
O7 | 0.0238 (7) | 0.0187 (7) | 0.0323 (8) | −0.0023 (6) | 0.0056 (6) | −0.0017 (6) |
O8 | 0.0342 (8) | 0.0264 (7) | 0.0288 (8) | −0.0061 (6) | 0.0160 (6) | −0.0073 (6) |
C1—C6 | 1.387 (2) | C14—H14 | 0.9500 |
C1—C2 | 1.389 (2) | C15—O6 | 1.3709 (19) |
C1—C7 | 1.514 (2) | C15—C16 | 1.386 (2) |
C2—C3 | 1.383 (2) | C16—O7 | 1.3814 (19) |
C2—H2 | 0.9500 | C16—C17 | 1.392 (2) |
C3—O2 | 1.3698 (18) | C17—O8 | 1.3699 (19) |
C3—C4 | 1.392 (2) | C17—C18 | 1.382 (2) |
C4—O3 | 1.3844 (18) | C18—H18 | 0.9500 |
C4—C5 | 1.392 (2) | C19—C20 | 1.529 (2) |
C5—O4 | 1.3692 (19) | C19—H19A | 0.9900 |
C5—C6 | 1.395 (2) | C19—H19B | 0.9900 |
C6—H6 | 0.9500 | C20—C21 | 1.509 (2) |
C7—C8 | 1.500 (2) | C20—H20A | 0.9900 |
C7—H7A | 0.9900 | C20—H20B | 0.9900 |
C7—H7B | 0.9900 | C21—O5 | 1.2397 (18) |
C8—C9 | 1.513 (2) | C21—N3 | 1.335 (2) |
C8—H8A | 0.9900 | C22—O6 | 1.4302 (19) |
C8—H8B | 0.9900 | C22—H22A | 0.9800 |
C9—O1 | 1.2438 (19) | C22—H22B | 0.9800 |
C9—N1 | 1.337 (2) | C22—H22C | 0.9800 |
C10—O2 | 1.4316 (19) | C23—O7 | 1.438 (2) |
C10—H10A | 0.9800 | C23—H23A | 0.9800 |
C10—H10B | 0.9800 | C23—H23B | 0.9800 |
C10—H10C | 0.9800 | C23—H23C | 0.9800 |
C11—O3 | 1.4350 (19) | C24—O8 | 1.4303 (19) |
C11—H11A | 0.9800 | C24—H24A | 0.9800 |
C11—H11B | 0.9800 | C24—H24B | 0.9800 |
C11—H11C | 0.9800 | C24—H24C | 0.9800 |
C12—O4 | 1.4349 (19) | N1—N2 | 1.4084 (18) |
C12—H12A | 0.9800 | N1—H1 | 0.8800 |
C12—H12B | 0.9800 | N2—H2A | 0.883 (17) |
C12—H12C | 0.9800 | N2—H2B | 1.016 (19) |
C13—C14 | 1.389 (2) | N3—N4 | 1.4177 (19) |
C13—C18 | 1.390 (2) | N3—H3 | 0.8800 |
C13—C19 | 1.513 (2) | N4—H4A | 0.997 (19) |
C14—C15 | 1.390 (2) | N4—H4B | 0.924 (18) |
C6—C1—C2 | 119.66 (16) | O7—C16—C15 | 120.21 (16) |
C6—C1—C7 | 123.41 (16) | O7—C16—C17 | 120.41 (16) |
C2—C1—C7 | 116.84 (16) | C15—C16—C17 | 119.33 (16) |
C3—C2—C1 | 120.52 (17) | O8—C17—C18 | 125.32 (16) |
C3—C2—H2 | 119.7 | O8—C17—C16 | 114.46 (16) |
C1—C2—H2 | 119.7 | C18—C17—C16 | 120.22 (16) |
O2—C3—C2 | 123.93 (16) | C17—C18—C13 | 120.56 (16) |
O2—C3—C4 | 115.88 (15) | C17—C18—H18 | 119.7 |
C2—C3—C4 | 120.17 (16) | C13—C18—H18 | 119.7 |
O3—C4—C3 | 119.86 (15) | C13—C19—C20 | 115.81 (14) |
O3—C4—C5 | 120.61 (16) | C13—C19—H19A | 108.3 |
C3—C4—C5 | 119.47 (16) | C20—C19—H19A | 108.3 |
O4—C5—C4 | 115.25 (15) | C13—C19—H19B | 108.3 |
O4—C5—C6 | 124.62 (16) | C20—C19—H19B | 108.3 |
C4—C5—C6 | 120.13 (16) | H19A—C19—H19B | 107.4 |
C1—C6—C5 | 120.00 (17) | C21—C20—C19 | 111.04 (14) |
C1—C6—H6 | 120.0 | C21—C20—H20A | 109.4 |
C5—C6—H6 | 120.0 | C19—C20—H20A | 109.4 |
C8—C7—C1 | 117.16 (15) | C21—C20—H20B | 109.4 |
C8—C7—H7A | 108.0 | C19—C20—H20B | 109.4 |
C1—C7—H7A | 108.0 | H20A—C20—H20B | 108.0 |
C8—C7—H7B | 108.0 | O5—C21—N3 | 122.02 (16) |
C1—C7—H7B | 108.0 | O5—C21—C20 | 122.26 (15) |
H7A—C7—H7B | 107.3 | N3—C21—C20 | 115.72 (15) |
C7—C8—C9 | 108.70 (14) | O6—C22—H22A | 109.5 |
C7—C8—H8A | 109.9 | O6—C22—H22B | 109.5 |
C9—C8—H8A | 109.9 | H22A—C22—H22B | 109.5 |
C7—C8—H8B | 109.9 | O6—C22—H22C | 109.5 |
C9—C8—H8B | 109.9 | H22A—C22—H22C | 109.5 |
H8A—C8—H8B | 108.3 | H22B—C22—H22C | 109.5 |
O1—C9—N1 | 122.40 (16) | O7—C23—H23A | 109.5 |
O1—C9—C8 | 122.22 (16) | O7—C23—H23B | 109.5 |
N1—C9—C8 | 115.37 (16) | H23A—C23—H23B | 109.5 |
O2—C10—H10A | 109.5 | O7—C23—H23C | 109.5 |
O2—C10—H10B | 109.5 | H23A—C23—H23C | 109.5 |
H10A—C10—H10B | 109.5 | H23B—C23—H23C | 109.5 |
O2—C10—H10C | 109.5 | O8—C24—H24A | 109.5 |
H10A—C10—H10C | 109.5 | O8—C24—H24B | 109.5 |
H10B—C10—H10C | 109.5 | H24A—C24—H24B | 109.5 |
O3—C11—H11A | 109.5 | O8—C24—H24C | 109.5 |
O3—C11—H11B | 109.5 | H24A—C24—H24C | 109.5 |
H11A—C11—H11B | 109.5 | H24B—C24—H24C | 109.5 |
O3—C11—H11C | 109.5 | C9—N1—N2 | 123.42 (14) |
H11A—C11—H11C | 109.5 | C9—N1—H1 | 118.3 |
H11B—C11—H11C | 109.5 | N2—N1—H1 | 118.3 |
O4—C12—H12A | 109.5 | N1—N2—H2A | 106.0 (11) |
O4—C12—H12B | 109.5 | N1—N2—H2B | 105.9 (10) |
H12A—C12—H12B | 109.5 | H2A—N2—H2B | 110.7 (15) |
O4—C12—H12C | 109.5 | C21—N3—N4 | 122.41 (14) |
H12A—C12—H12C | 109.5 | C21—N3—H3 | 118.8 |
H12B—C12—H12C | 109.5 | N4—N3—H3 | 118.8 |
C14—C13—C18 | 119.29 (16) | N3—N4—H4A | 106.5 (11) |
C14—C13—C19 | 122.19 (16) | N3—N4—H4B | 104.0 (11) |
C18—C13—C19 | 118.52 (15) | H4A—N4—H4B | 104.5 (15) |
C13—C14—C15 | 120.15 (16) | C3—O2—C10 | 116.49 (13) |
C13—C14—H14 | 119.9 | C4—O3—C11 | 113.23 (13) |
C15—C14—H14 | 119.9 | C5—O4—C12 | 117.30 (13) |
O6—C15—C16 | 115.50 (15) | C15—O6—C22 | 116.33 (13) |
O6—C15—C14 | 124.06 (16) | C16—O7—C23 | 113.08 (13) |
C16—C15—C14 | 120.44 (16) | C17—O8—C24 | 117.60 (14) |
C6—C1—C2—C3 | −1.8 (3) | O7—C16—C17—O8 | 2.4 (2) |
C7—C1—C2—C3 | 174.91 (16) | C15—C16—C17—O8 | 179.92 (15) |
C1—C2—C3—O2 | −178.38 (16) | O7—C16—C17—C18 | −177.00 (15) |
C1—C2—C3—C4 | 0.0 (3) | C15—C16—C17—C18 | 0.5 (3) |
O2—C3—C4—O3 | −2.5 (2) | O8—C17—C18—C13 | −178.71 (16) |
C2—C3—C4—O3 | 179.08 (14) | C16—C17—C18—C13 | 0.6 (3) |
O2—C3—C4—C5 | −179.66 (14) | C14—C13—C18—C17 | −1.0 (3) |
C2—C3—C4—C5 | 1.9 (2) | C19—C13—C18—C17 | 178.13 (16) |
O3—C4—C5—O4 | 0.8 (2) | C14—C13—C19—C20 | −14.5 (2) |
C3—C4—C5—O4 | 177.99 (15) | C18—C13—C19—C20 | 166.38 (15) |
O3—C4—C5—C6 | −179.06 (15) | C13—C19—C20—C21 | −168.65 (14) |
C3—C4—C5—C6 | −1.9 (2) | C19—C20—C21—O5 | 60.7 (2) |
C2—C1—C6—C5 | 1.8 (3) | C19—C20—C21—N3 | −119.84 (16) |
C7—C1—C6—C5 | −174.70 (16) | O1—C9—N1—N2 | −1.3 (3) |
O4—C5—C6—C1 | −179.80 (16) | C8—C9—N1—N2 | 177.26 (15) |
C4—C5—C6—C1 | 0.1 (3) | O5—C21—N3—N4 | −1.5 (3) |
C6—C1—C7—C8 | −7.2 (3) | C20—C21—N3—N4 | 179.07 (15) |
C2—C1—C7—C8 | 176.23 (16) | C2—C3—O2—C10 | −8.8 (2) |
C1—C7—C8—C9 | 178.66 (15) | C4—C3—O2—C10 | 172.76 (14) |
C7—C8—C9—O1 | 69.4 (2) | C3—C4—O3—C11 | 106.35 (18) |
C7—C8—C9—N1 | −109.15 (17) | C5—C4—O3—C11 | −76.49 (19) |
C18—C13—C14—C15 | 0.3 (3) | C4—C5—O4—C12 | 163.54 (14) |
C19—C13—C14—C15 | −178.80 (16) | C6—C5—O4—C12 | −16.6 (2) |
C13—C14—C15—O6 | −179.57 (15) | C16—C15—O6—C22 | 169.91 (15) |
C13—C14—C15—C16 | 0.8 (3) | C14—C15—O6—C22 | −9.7 (2) |
O6—C15—C16—O7 | −3.3 (2) | C15—C16—O7—C23 | 97.46 (19) |
C14—C15—C16—O7 | 176.30 (15) | C17—C16—O7—C23 | −85.0 (2) |
O6—C15—C16—C17 | 179.11 (15) | C18—C17—O8—C24 | 1.9 (3) |
C14—C15—C16—C17 | −1.2 (3) | C16—C17—O8—C24 | −177.41 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O6i | 0.924 (18) | 2.491 (19) | 3.401 (2) | 168.2 (15) |
N2—H2B···O5 | 1.016 (19) | 2.110 (19) | 3.045 (2) | 152.1 (14) |
N2—H2A···O3ii | 0.883 (17) | 2.618 (17) | 3.453 (2) | 158.2 (15) |
N2—H2A···O2ii | 0.883 (17) | 2.377 (17) | 3.067 (2) | 135.2 (14) |
N4—H4A···O1 | 0.997 (19) | 2.131 (19) | 3.084 (2) | 159.5 (15) |
N3—H3···O1iii | 0.88 | 2.02 | 2.8914 (18) | 171 |
N1—H1···O5iv | 0.88 | 2.01 | 2.8719 (18) | 166 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H18N2O4 |
Mr | 254.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 9.7770 (14), 20.189 (3), 12.7300 (19) |
β (°) | 99.618 (3) |
V (Å3) | 2477.4 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.20 × 0.05 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.980, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21411, 5897, 3183 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.077, 0.78 |
No. of reflections | 5897 |
No. of parameters | 347 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.20 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O6i | 0.924 (18) | 2.491 (19) | 3.401 (2) | 168.2 (15) |
N2—H2B···O5 | 1.016 (19) | 2.110 (19) | 3.045 (2) | 152.1 (14) |
N2—H2A···O3ii | 0.883 (17) | 2.618 (17) | 3.453 (2) | 158.2 (15) |
N2—H2A···O2ii | 0.883 (17) | 2.377 (17) | 3.067 (2) | 135.2 (14) |
N4—H4A···O1 | 0.997 (19) | 2.131 (19) | 3.084 (2) | 159.5 (15) |
N3—H3···O1iii | 0.88 | 2.02 | 2.8914 (18) | 170.8 |
N1—H1···O5iv | 0.88 | 2.01 | 2.8719 (18) | 166.0 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1; (iv) −x+1, −y, −z+1. |
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-mercapto-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, (I), and reported its crystal structure.
The asymmetric unit of the title compound, (I), contains two molecules (Fig. 1), in which the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar hydrazidic groups A (C9/O1/N1/N2), C (C21/O5/N3/N4) and benzene rings B (C1—C6), D (C13—C18) are A/B = 65.86 (2)° and C/D = 51.16 (2)°.
In the crystal structure, the intra- and intermolecular N—H···O hydrogen bonds link the molecules to form a supramolecular structure (Fig. 2).