N′-[(E)-(5-Methyl­furan-2-yl)methyl­idene]formohydrazide

Shafiq, Z.; Yaqub, M.; Tahir, M.N.; Nawaz, M.H.; Iqbal, M.S.

doi:10.1107/S1600536809037064

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2495

doi:10.1107/S1600536809037064

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N′-[(E)-(5-Methylfuran-2-yl)methylidene]formohydrazide

Zahid Shafiq,^a Muhammad Yaqub,^a M. Nawaz Tahir,^b ^* Mian Hasnain Nawaz ^a and M. Saeed Iqbal ^c

^aDepartment of Chemistry, Bahauddin Zakariya University, Multan 60800, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 12 September 2009; accepted 13 September 2009; online 19 September 2009)

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.

Related literature

For related structures, see: Shafiq et al. (2009 ); Bai & Jing (2007 ); Yao & Jing (2007 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₈N₂O₂
M_r = 152.15
Orthorhombic, P b c a
a = 10.6433 (14) Å
b = 6.7762 (8) Å
c = 21.129 (3) Å
V = 1523.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.25 × 0.15 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.985, T_max = 0.988
7485 measured reflections
1403 independent reflections
655 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.108
S = 1.00
1403 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.00	2.848 (3)	169
Symmetry code: (i) -x+1, -y+2, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037064/hb5099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037064/hb5099Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For related structures, see: Shafiq et al. (2009); Bai & Jing (2007); Yao & Jing (2007). For graph-set notaton, see: Bernstein et al. (1995).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radius.
	Fig. 2. The partial packing if (I) which shows that molecules are dimerized and form ring motifs.

N'-[(E)-(5-methylfuran-2-yl)methylidene]formohydrazide top

Crystal data top

C₇H₈N₂O₂	F(000) = 640
M_r = 152.15	D_x = 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 monochromator	R_int = 0.072
Detector resolution: 7.80 pixels mm^-1	θ_max = 25.5°, θ_min = 2.7°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→8
T_min = 0.985, T_max = 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(F_o²) + (0.0376P)²] where P = (F_o² + 2F_c²)/3
1403 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₈N₂O₂	V = 1523.9 (3) Å³
M_r = 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)
T_min = 0.985, T_max = 0.988	R_int = 0.072
7485 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.00	Δρ_max = 0.12 e Å⁻³
1403 reflections	Δρ_min = −0.16 e Å⁻³
101 parameters

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	U_iso*/U_eq
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, º) 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···C1^iv	3.461 (4)
O2···N2ⁱⁱ	2.848 (3)	C6···O2ⁱⁱⁱ	3.099 (3)
O2···C6ⁱ	3.099 (3)	C1···H7A^vii	3.0000
O1···H6ⁱⁱⁱ	2.8900	C2···H7A^vii	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···C2^iv	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···C6^v	3.461 (4)	H6···N1ⁱ	2.7000
C2···N2^v	3.408 (4)	H7A···C1^viii	3.0000
C5···C5^vi	3.595 (4)	H7A···C2^viii	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, º) 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 code: (ii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₂
M_r	152.15
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	10.6433 (14), 6.7762 (8), 21.129 (3)
V (Å³)	1523.9 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.15 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.985, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7485, 1403, 655
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.108, 1.00
No. of reflections	1403
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) 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 code: (i) −x+1, −y+2, −z.

Acknowledgements

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.

References

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