Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022593/hk2245sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022593/hk2245Isup2.hkl |
CCDC reference: 1233215
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.066
- wR factor = 0.109
- Data-to-parameter ratio = 20.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for N1 - N2 .. 20.22 su PLAT230_ALERT_2_B Hirshfeld Test Diff for N2 - C9 .. 21.22 su PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for N2
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 40 Perc. PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.12 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 - C2 .. 5.28 su PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1B ... ? PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... ?
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 7 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 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 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); Allen et al. (1987); Furniss et al. (1978).
The title compound, (I), is synthesized by reaction of the methyl ester of 3,5-difluorobenzoic acid with hydrazine hydrate using a reported procedure (Furniss et al., 1978). For the preparation of (I), a mixture of methyl-2,6-dimethoxybenzoate (1.96 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 1.78 g, 91%; m.p. 517–519 K). Colorless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.
H atoms were positioned geometrically, with N—H = 0.86 Å (for NH and NH2) and C—H = 0.93 and 0.96 Å for aromatic 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.
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the planar hydrazidic group (C9/O3/N1/N2) and benzene ring (C1—C6) is 97.07 (3)°.
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); 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: SHELXS97 (Sheldrick,1997); program(s) used to refine structure: SHELXL97 (Sheldrick,1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. The formation of the title compound. |
C9H12N2O3 | Dx = 1.257 Mg m−3 |
Mr = 196.21 | Melting point: 244(2) K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1520 reflections |
a = 7.2598 (5) Å | θ = 2.7–24.9° |
b = 14.2558 (11) Å | µ = 0.10 mm−1 |
c = 20.0412 (11) Å | T = 294 K |
V = 2074.1 (2) Å3 | Block, colourless |
Z = 8 | 0.16 × 0.14 × 0.06 mm |
F(000) = 832 |
Bruker APEXII diffractometer | 2615 independent reflections |
Radiation source: rotating-anode generator | 1044 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
φ and ω scans | θmax = 28.7°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.981, Tmax = 0.993 | k = −19→19 |
14489 measured reflections | l = −26→26 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + 0.1639P] where P = (Fo2 + 2Fc2)/3 |
S = 1.99 | (Δ/σ)max < 0.001 |
2615 reflections | Δρmax = 0.37 e Å−3 |
128 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick,1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0102 (7) |
C9H12N2O3 | V = 2074.1 (2) Å3 |
Mr = 196.21 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.2598 (5) Å | µ = 0.10 mm−1 |
b = 14.2558 (11) Å | T = 294 K |
c = 20.0412 (11) Å | 0.16 × 0.14 × 0.06 mm |
Bruker APEXII diffractometer | 2615 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1044 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.993 | Rint = 0.043 |
14489 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.99 | Δρmax = 0.37 e Å−3 |
2615 reflections | Δρmin = −0.40 e Å−3 |
128 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 | ||
O1 | −0.0885 (3) | 0.45612 (13) | 0.41648 (11) | 0.0982 (7) | |
O2 | 0.4159 (3) | 0.29139 (14) | 0.33521 (9) | 0.0827 (6) | |
O3 | −0.0195 (3) | 0.24193 (13) | 0.37742 (10) | 0.0873 (6) | |
N1 | 0.1159 (4) | 0.1846 (2) | 0.49375 (14) | 0.1344 (12) | |
H1A | 0.0378 | 0.1475 | 0.4751 | 0.161* | |
H1B | 0.1633 | 0.1701 | 0.5317 | 0.161* | |
N2 | 0.1671 (3) | 0.27065 (13) | 0.46145 (9) | 0.0542 (5) | |
H2A | 0.2450 | 0.3082 | 0.4796 | 0.065* | |
C1 | 0.1691 (4) | 0.37920 (17) | 0.37441 (12) | 0.0623 (7) | |
C2 | 0.0721 (5) | 0.4629 (2) | 0.38130 (15) | 0.0787 (9) | |
C3 | 0.1419 (6) | 0.5447 (2) | 0.35300 (17) | 0.1006 (11) | |
H3A | 0.0796 | 0.6014 | 0.3575 | 0.121* | |
C4 | 0.3060 (6) | 0.5399 (3) | 0.31813 (17) | 0.1075 (13) | |
H4A | 0.3530 | 0.5945 | 0.2994 | 0.129* | |
C5 | 0.4017 (5) | 0.4583 (3) | 0.31005 (15) | 0.0969 (11) | |
H5A | 0.5103 | 0.4572 | 0.2855 | 0.116* | |
C6 | 0.3336 (4) | 0.3771 (2) | 0.33932 (13) | 0.0713 (8) | |
C7 | −0.1954 (5) | 0.5395 (2) | 0.42662 (18) | 0.1352 (15) | |
H7A | −0.3034 | 0.5246 | 0.4522 | 0.203* | |
H7B | −0.2314 | 0.5648 | 0.3842 | 0.203* | |
H7C | −0.1230 | 0.5850 | 0.4503 | 0.203* | |
C8 | 0.5861 (4) | 0.2843 (2) | 0.29912 (15) | 0.1081 (11) | |
H8A | 0.6286 | 0.2205 | 0.3001 | 0.162* | |
H8B | 0.6766 | 0.3243 | 0.3194 | 0.162* | |
H8C | 0.5670 | 0.3034 | 0.2537 | 0.162* | |
C9 | 0.0935 (4) | 0.29037 (18) | 0.40452 (14) | 0.0637 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1089 (17) | 0.0674 (13) | 0.1182 (17) | 0.0212 (13) | 0.0054 (15) | −0.0019 (12) |
O2 | 0.0755 (14) | 0.0910 (15) | 0.0816 (13) | −0.0016 (12) | 0.0144 (11) | 0.0078 (11) |
O3 | 0.0909 (15) | 0.0748 (13) | 0.0963 (15) | −0.0186 (12) | −0.0211 (12) | 0.0075 (11) |
N1 | 0.128 (3) | 0.142 (3) | 0.133 (3) | −0.016 (2) | −0.016 (2) | 0.043 (2) |
N2 | 0.0614 (13) | 0.0551 (12) | 0.0461 (11) | −0.0188 (11) | −0.0156 (11) | 0.0142 (10) |
C1 | 0.0708 (19) | 0.0545 (16) | 0.0617 (17) | −0.0057 (16) | −0.0072 (16) | −0.0024 (14) |
C2 | 0.096 (2) | 0.0639 (19) | 0.077 (2) | −0.0052 (19) | −0.0124 (19) | −0.0016 (17) |
C3 | 0.137 (3) | 0.060 (2) | 0.104 (3) | −0.011 (2) | −0.031 (2) | 0.0052 (19) |
C4 | 0.139 (4) | 0.082 (3) | 0.102 (3) | −0.043 (3) | −0.019 (3) | 0.024 (2) |
C5 | 0.109 (3) | 0.092 (2) | 0.090 (2) | −0.032 (2) | −0.007 (2) | 0.016 (2) |
C6 | 0.082 (2) | 0.0689 (19) | 0.0632 (18) | −0.0172 (18) | −0.0092 (17) | 0.0040 (16) |
C7 | 0.149 (4) | 0.092 (3) | 0.164 (4) | 0.052 (3) | −0.001 (3) | −0.017 (2) |
C8 | 0.082 (2) | 0.138 (3) | 0.104 (2) | −0.002 (2) | 0.027 (2) | 0.016 (2) |
C9 | 0.0566 (17) | 0.0564 (17) | 0.078 (2) | 0.0001 (14) | 0.0090 (16) | −0.0064 (15) |
O1—C2 | 1.366 (3) | C2—C3 | 1.393 (4) |
O1—C7 | 1.434 (3) | C3—C4 | 1.383 (4) |
O2—C6 | 1.362 (3) | C3—H3A | 0.9300 |
O2—C8 | 1.436 (3) | C4—C5 | 1.364 (4) |
O3—C9 | 1.202 (3) | C4—H4A | 0.9300 |
N1—N2 | 1.436 (3) | C5—C6 | 1.390 (4) |
N1—H1A | 0.8600 | C5—H5A | 0.9300 |
N1—H1B | 0.8600 | C7—H7A | 0.9600 |
N2—C9 | 1.291 (3) | C7—H7B | 0.9600 |
N2—H2A | 0.8600 | C7—H7C | 0.9600 |
C1—C6 | 1.386 (3) | C8—H8A | 0.9600 |
C1—C2 | 1.393 (3) | C8—H8B | 0.9600 |
C1—C9 | 1.506 (3) | C8—H8C | 0.9600 |
C2—O1—C7 | 118.4 (3) | C4—C5—H5A | 120.7 |
C6—O2—C8 | 118.1 (2) | C6—C5—H5A | 120.7 |
N2—N1—H1A | 120.0 | O2—C6—C5 | 124.5 (3) |
N2—N1—H1B | 120.0 | O2—C6—C1 | 115.3 (3) |
H1A—N1—H1B | 120.0 | C5—C6—C1 | 120.2 (3) |
C9—N2—N1 | 118.5 (2) | O1—C7—H7A | 109.5 |
C9—N2—H2A | 120.7 | O1—C7—H7B | 109.5 |
N1—N2—H2A | 120.7 | H7A—C7—H7B | 109.5 |
C6—C1—C2 | 120.3 (3) | O1—C7—H7C | 109.5 |
C6—C1—C9 | 119.9 (2) | H7A—C7—H7C | 109.5 |
C2—C1—C9 | 119.7 (3) | H7B—C7—H7C | 109.5 |
O1—C2—C3 | 125.5 (3) | O2—C8—H8A | 109.5 |
O1—C2—C1 | 115.0 (3) | O2—C8—H8B | 109.5 |
C3—C2—C1 | 119.5 (3) | H8A—C8—H8B | 109.5 |
C2—C3—C4 | 118.5 (3) | O2—C8—H8C | 109.5 |
C2—C3—H3A | 120.7 | H8A—C8—H8C | 109.5 |
C4—C3—H3A | 120.7 | H8B—C8—H8C | 109.5 |
C5—C4—C3 | 122.8 (3) | O3—C9—N2 | 123.8 (3) |
C5—C4—H4A | 118.6 | O3—C9—C1 | 123.4 (3) |
C3—C4—H4A | 118.6 | N2—C9—C1 | 112.7 (2) |
C4—C5—C6 | 118.6 (3) |
Experimental details
Crystal data | |
Chemical formula | C9H12N2O3 |
Mr | 196.21 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 7.2598 (5), 14.2558 (11), 20.0412 (11) |
V (Å3) | 2074.1 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.16 × 0.14 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.981, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14489, 2615, 1044 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.675 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.109, 1.99 |
No. of reflections | 2615 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.40 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick,1997), SHELXL97 (Sheldrick,1997), SHELXTL (Bruker, 1999), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
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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-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.
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the planar hydrazidic group (C9/O3/N1/N2) and benzene ring (C1—C6) is 97.07 (3)°.