supplementary materials
N'-[(E)-(5-Methylfuran-2-yl)methylidene]formohydrazide
The title compound, C7H8N2O2, is almost planar (r.m.s. deviation for non-H atoms = 0.029 Å). In the crystal, inversion dimers linked by pairs of N-H
O hydrogen bonds generate an R22(8) ring motif.
To a hot stirred solution of formohydrazide (1.0 g, 0.017 mol) in ethanol (10 ml) was added 5-methylfurfural (1.65 ml, 0.017 mol). The resultant mixture was
then heated under reflux for 4 h and monitored through TLC. After completion
of reaction, the mixture was cooled to room temperature. The crude solid was
collected by suction filtration. The precipitates were washed with hot
ethanol, filtered and dried. Brown needles of (I) were
obtained by recrystalization from (1:1 v/v) methanol:1,4-dioxan.
The H-atoms were positioned geometrically with N—H = 0.86, C—H = 0.93 and
0.96 Å for aryl 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.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
N'-[(
E)-(5-methylfuran-2-yl)methylidene]formohydrazide
top
Crystal data top
| C7H8N2O2 | F(000) = 640 |
| Mr = 152.15 | Dx = 1.326 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1864 reflections |
| a = 10.6433 (14) Å | θ = 2.7–25.5° |
| b = 6.7762 (8) Å | µ = 0.10 mm−1 |
| c = 21.129 (3) Å | T = 296 K |
| V = 1523.9 (3) Å3 | Cut needle, brown |
| Z = 8 | 0.25 × 0.15 × 0.13 mm |
Data collection top
Bruker Kappa APEXII CCD
diffractometer | 1403 independent reflections |
| Radiation source: fine-focus sealed tube | 655 reflections with I > 2σ(I) |
| graphite | Rint = 0.072 |
| Detector resolution: 7.80 pixels mm-1 | θmax = 25.5°, θmin = 2.7° |
| ω scans | h = −12→12 |
Absorption correction: multi-scan
(SADABS; Bruker, 2005) | k = −5→8 |
| Tmin = 0.985, Tmax = 0.988 | l = −23→25 |
| 7485 measured reflections | |
Refinement top
| 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.108 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0376P)2]
where P = (Fo2 + 2Fc2)/3 |
| 1403 reflections | (Δ/σ)max < 0.001 |
| 101 parameters | Δρmax = 0.12 e Å−3 |
| 0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
| C7H8N2O2 | V = 1523.9 (3) Å3 |
| Mr = 152.15 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 10.6433 (14) Å | µ = 0.10 mm−1 |
| b = 6.7762 (8) Å | T = 296 K |
| c = 21.129 (3) Å | 0.25 × 0.15 × 0.13 mm |
Data collection top
Bruker Kappa APEXII CCD
diffractometer | 1403 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2005) | 655 reflections with I > 2σ(I) |
| Tmin = 0.985, Tmax = 0.988 | Rint = 0.072 |
| 7485 measured reflections | θmax = 25.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
| wR(F2) = 0.108 | Δρmax = 0.12 e Å−3 |
| S = 1.00 | Δρmin = −0.16 e Å−3 |
| 1403 reflections | Absolute structure: ? |
| 101 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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| | x | y | z | Uiso*/Ueq | |
| O1 | 0.56771 (16) | 0.2958 (2) | 0.15544 (8) | 0.0550 (7) | |
| O2 | 0.66434 (16) | 1.0759 (3) | 0.01153 (9) | 0.0665 (8) | |
| N1 | 0.5699 (2) | 0.6414 (3) | 0.08604 (10) | 0.0486 (8) | |
| N2 | 0.56384 (19) | 0.8059 (3) | 0.04784 (10) | 0.0497 (8) | |
| C1 | 0.5376 (3) | 0.1184 (4) | 0.18332 (14) | 0.0602 (11) | |
| C2 | 0.4218 (3) | 0.0664 (4) | 0.16579 (15) | 0.0717 (14) | |
| C3 | 0.3762 (3) | 0.2130 (4) | 0.12461 (15) | 0.0641 (11) | |
| C4 | 0.4667 (2) | 0.3504 (4) | 0.11942 (12) | 0.0481 (10) | |
| C5 | 0.4735 (2) | 0.5290 (4) | 0.08350 (13) | 0.0501 (10) | |
| C6 | 0.6618 (2) | 0.9277 (4) | 0.04483 (14) | 0.0542 (11) | |
| C7 | 0.6371 (3) | 0.0296 (4) | 0.22318 (15) | 0.0950 (16) | |
| H2 | 0.37892 | −0.04640 | 0.17850 | 0.0858* | |
| H2A | 0.49724 | 0.82967 | 0.02609 | 0.0596* | |
| H3 | 0.29823 | 0.21455 | 0.10475 | 0.0770* | |
| H5 | 0.40630 | 0.56423 | 0.05772 | 0.0599* | |
| H6 | 0.73203 | 0.89887 | 0.06930 | 0.0651* | |
| H7A | 0.61090 | −0.09910 | 0.23690 | 0.1421* | |
| H7B | 0.71316 | 0.01834 | 0.19904 | 0.1421* | |
| H7C | 0.65168 | 0.11181 | 0.25943 | 0.1421* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O1 | 0.0546 (12) | 0.0537 (12) | 0.0566 (13) | −0.0005 (9) | 0.0025 (11) | 0.0096 (10) |
| O2 | 0.0620 (14) | 0.0531 (12) | 0.0845 (17) | −0.0070 (9) | −0.0148 (11) | 0.0163 (11) |
| N1 | 0.0461 (14) | 0.0486 (13) | 0.0510 (16) | 0.0081 (12) | 0.0010 (12) | 0.0037 (12) |
| N2 | 0.0408 (13) | 0.0512 (13) | 0.0570 (16) | 0.0048 (12) | −0.0071 (12) | 0.0094 (12) |
| C1 | 0.074 (2) | 0.0447 (18) | 0.062 (2) | 0.0016 (16) | 0.0148 (19) | 0.0060 (16) |
| C2 | 0.080 (2) | 0.054 (2) | 0.081 (3) | −0.0146 (18) | 0.025 (2) | −0.0025 (17) |
| C3 | 0.0533 (19) | 0.068 (2) | 0.071 (2) | −0.0095 (17) | 0.0073 (17) | −0.0096 (18) |
| C4 | 0.0415 (16) | 0.0546 (19) | 0.0483 (19) | 0.0013 (15) | 0.0047 (14) | −0.0011 (15) |
| C5 | 0.0416 (16) | 0.0567 (18) | 0.052 (2) | 0.0088 (14) | −0.0007 (14) | 0.0003 (15) |
| C6 | 0.0454 (18) | 0.0562 (18) | 0.061 (2) | 0.0042 (15) | −0.0088 (16) | −0.0033 (17) |
| C7 | 0.116 (3) | 0.081 (2) | 0.088 (3) | 0.018 (2) | −0.004 (2) | 0.031 (2) |
Geometric parameters (Å, °) top
| O1—C1 | 1.377 (3) | C3—C4 | 1.344 (4) |
| O1—C4 | 1.368 (3) | C4—C5 | 1.430 (4) |
| O2—C6 | 1.227 (3) | C2—H2 | 0.9300 |
| N1—N2 | 1.378 (3) | C3—H3 | 0.9300 |
| N1—C5 | 1.279 (3) | C5—H5 | 0.9300 |
| N2—C6 | 1.331 (3) | C6—H6 | 0.9300 |
| N2—H2A | 0.8600 | C7—H7A | 0.9600 |
| C1—C2 | 1.334 (4) | C7—H7B | 0.9600 |
| C1—C7 | 1.481 (4) | C7—H7C | 0.9600 |
| C2—C3 | 1.407 (4) | | |
| | | |
| O1···N1 | 2.763 (3) | C6···N1i | 3.318 (3) |
| O2···N1i | 3.268 (3) | C6···C1iv | 3.461 (4) |
| O2···N2ii | 2.848 (3) | C6···O2iii | 3.099 (3) |
| O2···C6i | 3.099 (3) | C1···H7Avii | 3.0000 |
| O1···H6iii | 2.8900 | C2···H7Avii | 3.0800 |
| O2···H2Aii | 2.0000 | C6···H2Aii | 2.8000 |
| O2···H6i | 2.7400 | H2A···H5 | 2.1500 |
| N1···O1 | 2.763 (3) | H2A···O2ii | 2.0000 |
| N1···O2iii | 3.268 (3) | H2A···C6ii | 2.8000 |
| N1···C6iii | 3.318 (3) | H2A···H2Aii | 2.5600 |
| N2···C2iv | 3.408 (4) | H5···H2A | 2.1500 |
| N2···O2ii | 2.848 (3) | H6···O1i | 2.8900 |
| N1···H6iii | 2.7000 | H6···O2iii | 2.7400 |
| C1···C6v | 3.461 (4) | H6···N1i | 2.7000 |
| C2···N2v | 3.408 (4) | H7A···C1viii | 3.0000 |
| C5···C5vi | 3.595 (4) | H7A···C2viii | 3.0800 |
| | | |
| C1—O1—C4 | 106.9 (2) | C1—C2—H2 | 126.00 |
| N2—N1—C5 | 114.8 (2) | C3—C2—H2 | 126.00 |
| N1—N2—C6 | 119.5 (2) | C2—C3—H3 | 127.00 |
| N1—N2—H2A | 120.00 | C4—C3—H3 | 127.00 |
| C6—N2—H2A | 120.00 | N1—C5—H5 | 119.00 |
| C2—C1—C7 | 135.3 (3) | C4—C5—H5 | 119.00 |
| O1—C1—C2 | 109.1 (2) | O2—C6—H6 | 118.00 |
| O1—C1—C7 | 115.6 (2) | N2—C6—H6 | 118.00 |
| C1—C2—C3 | 107.7 (3) | C1—C7—H7A | 109.00 |
| C2—C3—C4 | 107.0 (3) | C1—C7—H7B | 109.00 |
| O1—C4—C5 | 119.0 (2) | C1—C7—H7C | 109.00 |
| O1—C4—C3 | 109.3 (2) | H7A—C7—H7B | 109.00 |
| C3—C4—C5 | 131.7 (2) | H7A—C7—H7C | 109.00 |
| N1—C5—C4 | 121.5 (2) | H7B—C7—H7C | 110.00 |
| O2—C6—N2 | 123.5 (2) | | |
| | | |
| C4—O1—C1—C2 | −0.7 (3) | O1—C1—C2—C3 | 0.9 (3) |
| C4—O1—C1—C7 | 178.2 (2) | C7—C1—C2—C3 | −177.7 (3) |
| C1—O1—C4—C3 | 0.2 (3) | C1—C2—C3—C4 | −0.7 (4) |
| C1—O1—C4—C5 | −178.5 (2) | C2—C3—C4—O1 | 0.3 (3) |
| C5—N1—N2—C6 | −177.0 (2) | C2—C3—C4—C5 | 178.8 (3) |
| N2—N1—C5—C4 | 178.7 (2) | O1—C4—C5—N1 | −2.4 (4) |
| N1—N2—C6—O2 | 179.2 (2) | C3—C4—C5—N1 | 179.2 (3) |
| Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1, −y+2, −z; (iii) −x+3/2, y−1/2, z; (iv) x, y+1, z; (v) x, y−1, z; (vi) −x+1, −y+1, −z; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2ii | 0.86 | 2.00 | 2.848 (3) | 169 |
| Symmetry codes: (ii) −x+1, −y+2, −z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2i | 0.86 | 2.00 | 2.848 (3) | 169 |
| Symmetry codes: (i) −x+1, −y+2, −z. |
The authors acknowledge the Higher Education Commission, Islamabad, Pakistan,
and Bana International, Karachi, Pakistan, for funding the purchase of the
diffractometer at GCU, Lahore and for technical support, respectively.
Bai, Z.-C. & Jing, Z.-L. (2007). Acta Cryst. E63, o3822.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Shafiq, Z., Yaqub, M., Tahir, M. N., Nawaz, M. H. & Iqbal, M. S. (2009). Acta Cryst. E65, BQ2157.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Yao, X.-L. & Jing, Z.-L. (2007). Acta Cryst. E63, o3900.
![[Figure 1]](./hb5099fig1thm.gif)
![[Figure 2]](./hb5099fig2thm.gif)
In continuation of our studies of different derivatives of formohydrazide (Shafiq et al., 2009), the title compound (I, Fig. 1), has been prepared and being reported. The metal complexes of (I) has been prepared with transition metals and their various studies are in progress.
The crystal structures of (II) (E)-4-bromo-N'-((5-methylfuran-2-yl)methylene)benzohydrazide (Bai & Jing, 2007), (III) (E)-N'-((5-methylfuran-2-yl)methylene)furan-2-carbohydrazide (Yao & Jing, 2007) have been reported which contain the 5-methylfuran-2-yl moiety as present in (I). The title compound consists of dimers due to intermolecular H-bonding of type N–H···O (Table 1, Fig. 2) forming R22(8) (Bernstein et al., 1995) ring motif. Similar bonding also exist in N'-[(1E)-1-(4-Chlorophenyl)ethylidene]formohydrazide (Shafiq et al., 2009). The overall molecule of (I) is planar with an r.m.s. deviation of 0.0285 Å.