2-[(E)-3,4-Dimeth­oxy­benzyl­idene]hydrazinecarboxamide

Tahir, M.N.; Umar, M.N.; Ali, A.; Shad, H.A.

doi:10.1107/S1600536812020739

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1724

doi:10.1107/S1600536812020739

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2-[(E)-3,4-Dimethoxybenzylidene]hydrazinecarboxamide

M. Nawaz Tahir,^a ^* M. Naveed Umar,^b Akbar Ali ^b and Hazoor Ahmad Shad ^c

^aUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, ^bDepartment of Chemistry, University of Malakand, Pakistan, and ^cDepartment of Chemistry, Government Post Graduate College, Gojra, Punjab, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 7 May 2012; accepted 8 May 2012; online 16 May 2012)

In the title compound, C₁₀H₁₃N₃O₃, the 3,4-dimethoxybenzylidene and hydrazinecarboxamide groups are oriented at a dihedral angle of 53.82 (6)° and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring motif. In the crystal, molecules are linked by N—H⋯O hydrogen bonds into sheets propagating in (-201), which feature R₁²(5), R₂²(8) and R₂⁴(14) loops.

Related literature

For related structures, see: Fun et al. (2011 ); Liang et al. (2007 ); For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₃N₃O₃
M_r = 223.23
Monoclinic, C 2/c
a = 22.2300 (7) Å
b = 7.6367 (3) Å
c = 15.6482 (6) Å
β = 126.234 (1)°
V = 2142.76 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.975, T_max = 0.985
7933 measured reflections
2115 independent reflections
1389 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.121
S = 1.01
2115 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.86	2.15	2.970 (2)	159
N3—H3A⋯O3ⁱⁱ	0.86	2.19	3.044 (2)	170
N3—H3B⋯N1	0.86	2.30	2.657 (2)	105
N3—H3B⋯O1ⁱⁱⁱ	0.86	2.59	3.019 (2)	112
N3—H3B⋯O2ⁱⁱⁱ	0.86	2.30	3.119 (2)	160
Symmetry codes: (i) -x, -y, -z; (ii) -x, -y+1, -z; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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/S1600536812020739/hb6783sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020739/hb6783Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020739/hb6783Isup3.cml

checkCIF report

Comment top

The title compound (I), (Fig. 1) has been synthesized as a derivative.

The crystal structures of (E)-1-(4-methoxybenzylidene)semicarbazide (Liang et al., 2007) and (E)-2-(4-hydroxy-3-methoxybenzylidene) hydrazinecarboxamide (Fun et al., 2011) have been published which are related to the title compound (I).

In (I), the parts of 3,4-dimethoxybenzaldehyde and hydrazinecarboxamide A (C1—C9/O1/O2) and B (N1/N2/C10/N3/O3), are almost planar with r. m. s. deviation of 0.0770 and 0.0159 Å, respectively. The dihedral angle between A/B is 53.82 (6)°. There exist intramolecular H–bonding of N—H···N type (Table 1, Fig. 1) and form S(5) ring motif (Bernstein et al., 1995). Each molecule is interlinked with three molecules due to H-bondings of N—H···O type. There exist R₁²(5), R₂²(8) and R₂⁴(14) ring motifs (Table 1, Fig. 2). The molecules are interliked in the form of two-dimensional polymeric sheets in the plane (201) and with base vectors [100] and [102].

Related literature top

For related structures, see: Fun et al. (2011); Liang et al. (2007); For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Equimolar quantities of 3,4-dimethoxybenzaldehyde and hydrazinecarboxamide were refluxed in methanol for 45 min resulting in yellow solution. The solution was kept at room temperature which affoarded yellow prisms after 48 h.

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 the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted lines indicate the intra-molecular hydrogen bond.
	Fig. 2. Partial packnig diagram showing molecules interlinked to form polymeric sheets with various ring motifs.

2-[(E)-3,4-Dimethoxybenzylidene]hydrazinecarboxamide top

Crystal data top

C₁₀H₁₃N₃O₃	F(000) = 944
M_r = 223.23	D_x = 1.384 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1389 reflections
a = 22.2300 (7) Å	θ = 2.3–26.0°
b = 7.6367 (3) Å	µ = 0.10 mm⁻¹
c = 15.6482 (6) Å	T = 296 K
β = 126.234 (1)°	Prism, yellow
V = 2142.76 (14) Å³	0.25 × 0.18 × 0.15 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	2115 independent reflections
Radiation source: fine-focus sealed tube	1389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8.00 pixels mm^-1	θ_max = 26.0°, θ_min = 2.3°
ω scans	h = −26→27
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
T_min = 0.975, T_max = 0.985	l = −19→19
7933 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0592P)² + 0.0283P] where P = (F_o² + 2F_c²)/3
2115 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₀H₁₃N₃O₃	V = 2142.76 (14) Å³
M_r = 223.23	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.2300 (7) Å	µ = 0.10 mm⁻¹
b = 7.6367 (3) Å	T = 296 K
c = 15.6482 (6) Å	0.25 × 0.18 × 0.15 mm
β = 126.234 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2115 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1389 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.985	R_int = 0.040
7933 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.01	Δρ_max = 0.16 e Å⁻³
2115 reflections	Δρ_min = −0.20 e Å⁻³
147 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	0.30582 (7)	−0.13305 (19)	0.72476 (10)	0.0464 (5)
O2	0.34785 (7)	0.03543 (19)	0.62646 (10)	0.0454 (5)
O3	−0.01303 (7)	0.24827 (17)	−0.02345 (10)	0.0447 (5)
N1	0.10093 (8)	0.0967 (2)	0.23838 (12)	0.0404 (5)
N2	0.04892 (8)	0.0982 (2)	0.12929 (12)	0.0421 (5)
N3	0.06302 (9)	0.3952 (2)	0.13090 (13)	0.0445 (6)
C1	0.15297 (10)	−0.0591 (2)	0.40077 (15)	0.0347 (6)
C2	0.22548 (10)	0.0085 (2)	0.45703 (15)	0.0356 (6)
C3	0.27503 (10)	−0.0179 (2)	0.56479 (14)	0.0331 (6)
C4	0.25221 (10)	−0.1097 (2)	0.61917 (15)	0.0345 (6)
C5	0.18023 (10)	−0.1725 (3)	0.56366 (15)	0.0394 (7)
C6	0.13153 (10)	−0.1495 (3)	0.45538 (15)	0.0397 (7)
C7	0.28984 (13)	−0.2490 (3)	0.78007 (16)	0.0527 (8)
C8	0.37782 (11)	0.1099 (3)	0.57544 (17)	0.0490 (8)
C9	0.10014 (10)	−0.0369 (3)	0.28603 (15)	0.0400 (7)
C10	0.03155 (9)	0.2502 (3)	0.07501 (15)	0.0347 (6)
H2	0.24028	0.07157	0.42152	0.0427*
H2A	0.02764	0.00235	0.09601	0.0505*
H3A	0.05296	0.49443	0.09922	0.0534*
H3B	0.09351	0.38993	0.19885	0.0534*
H5	0.16442	−0.23070	0.59936	0.0473*
H6	0.08359	−0.19543	0.41857	0.0476*
H7A	0.24962	−0.20238	0.77979	0.0791*
H7B	0.33332	−0.26156	0.85185	0.0791*
H7C	0.27580	−0.36131	0.74591	0.0791*
H8A	0.35195	0.21675	0.54077	0.0735*
H8B	0.37181	0.02896	0.52397	0.0735*
H8C	0.42987	0.13423	0.62723	0.0735*
H9	0.06472	−0.12360	0.24658	0.0479*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0482 (8)	0.0532 (9)	0.0289 (8)	−0.0080 (7)	0.0179 (7)	0.0017 (7)
O2	0.0369 (8)	0.0576 (9)	0.0338 (8)	−0.0152 (7)	0.0165 (7)	−0.0050 (7)
O3	0.0471 (8)	0.0416 (9)	0.0264 (7)	0.0006 (6)	0.0113 (7)	−0.0004 (6)
N1	0.0408 (9)	0.0384 (10)	0.0272 (9)	0.0008 (7)	0.0120 (8)	−0.0009 (7)
N2	0.0448 (10)	0.0355 (9)	0.0263 (9)	−0.0042 (8)	0.0102 (8)	−0.0018 (7)
N3	0.0476 (10)	0.0351 (10)	0.0320 (10)	−0.0030 (8)	0.0132 (8)	−0.0010 (7)
C1	0.0362 (10)	0.0307 (10)	0.0330 (11)	0.0031 (8)	0.0181 (9)	−0.0009 (8)
C2	0.0401 (11)	0.0327 (11)	0.0345 (11)	−0.0023 (8)	0.0224 (9)	−0.0013 (8)
C3	0.0321 (10)	0.0330 (10)	0.0303 (11)	−0.0042 (8)	0.0163 (9)	−0.0062 (8)
C4	0.0374 (10)	0.0335 (10)	0.0304 (10)	0.0001 (8)	0.0188 (9)	−0.0022 (8)
C5	0.0417 (11)	0.0418 (12)	0.0394 (12)	−0.0001 (9)	0.0266 (10)	0.0031 (9)
C6	0.0307 (10)	0.0406 (12)	0.0421 (12)	0.0005 (9)	0.0184 (9)	0.0015 (9)
C7	0.0604 (14)	0.0619 (16)	0.0364 (12)	−0.0022 (11)	0.0289 (11)	0.0071 (11)
C8	0.0462 (12)	0.0524 (14)	0.0524 (14)	−0.0126 (10)	0.0313 (12)	−0.0047 (11)
C9	0.0350 (11)	0.0397 (12)	0.0337 (11)	−0.0015 (9)	0.0140 (10)	−0.0014 (9)
C10	0.0289 (10)	0.0391 (11)	0.0294 (10)	−0.0001 (8)	0.0136 (9)	−0.0010 (9)

Geometric parameters (Å, º) top

O1—C4	1.362 (2)	C2—C3	1.379 (3)
O1—C7	1.422 (3)	C3—C4	1.408 (3)
O2—C3	1.368 (3)	C4—C5	1.379 (3)
O2—C8	1.426 (3)	C5—C6	1.380 (3)
O3—C10	1.245 (2)	C2—H2	0.9300
N1—N2	1.385 (2)	C5—H5	0.9300
N1—C9	1.270 (3)	C6—H6	0.9300
N2—C10	1.353 (3)	C7—H7A	0.9600
N3—C10	1.326 (3)	C7—H7B	0.9600
N2—H2A	0.8600	C7—H7C	0.9600
N3—H3A	0.8600	C8—H8A	0.9600
N3—H3B	0.8600	C8—H8B	0.9600
C1—C9	1.463 (3)	C8—H8C	0.9600
C1—C2	1.401 (3)	C9—H9	0.9300
C1—C6	1.384 (3)

C4—O1—C7	117.75 (18)	N2—C10—N3	117.33 (17)
C3—O2—C8	118.26 (15)	O3—C10—N2	119.32 (19)
N2—N1—C9	116.05 (17)	C1—C2—H2	120.00
N1—N2—C10	120.10 (15)	C3—C2—H2	120.00
N1—N2—H2A	120.00	C4—C5—H5	120.00
C10—N2—H2A	120.00	C6—C5—H5	120.00
C10—N3—H3A	120.00	C1—C6—H6	120.00
C10—N3—H3B	120.00	C5—C6—H6	120.00
H3A—N3—H3B	120.00	O1—C7—H7A	109.00
C2—C1—C6	118.95 (18)	O1—C7—H7B	109.00
C2—C1—C9	121.3 (2)	O1—C7—H7C	109.00
C6—C1—C9	119.7 (2)	H7A—C7—H7B	109.00
C1—C2—C3	120.4 (2)	H7A—C7—H7C	109.00
C2—C3—C4	119.9 (2)	H7B—C7—H7C	109.00
O2—C3—C4	114.88 (16)	O2—C8—H8A	109.00
O2—C3—C2	125.2 (2)	O2—C8—H8B	109.00
O1—C4—C5	125.2 (2)	O2—C8—H8C	109.00
O1—C4—C3	115.4 (2)	H8A—C8—H8B	109.00
C3—C4—C5	119.39 (18)	H8A—C8—H8C	109.00
C4—C5—C6	120.3 (2)	H8B—C8—H8C	109.00
C1—C6—C5	121.0 (2)	N1—C9—H9	119.00
N1—C9—C1	122.29 (19)	C1—C9—H9	119.00
O3—C10—N3	123.4 (2)

C7—O1—C4—C3	−169.75 (18)	C2—C1—C9—N1	−31.7 (3)
C7—O1—C4—C5	8.3 (3)	C6—C1—C9—N1	148.8 (2)
C8—O2—C3—C2	−6.2 (3)	C1—C2—C3—O2	176.97 (18)
C8—O2—C3—C4	172.38 (17)	C1—C2—C3—C4	−1.5 (3)
C9—N1—N2—C10	162.2 (2)	O2—C3—C4—O1	−0.4 (2)
N2—N1—C9—C1	178.4 (2)	O2—C3—C4—C5	−178.58 (18)
N1—N2—C10—O3	177.1 (2)	C2—C3—C4—O1	178.23 (17)
N1—N2—C10—N3	−3.6 (3)	C2—C3—C4—C5	0.1 (3)
C6—C1—C2—C3	1.3 (3)	O1—C4—C5—C6	−176.4 (2)
C9—C1—C2—C3	−178.29 (19)	C3—C4—C5—C6	1.6 (3)
C2—C1—C6—C5	0.4 (3)	C4—C5—C6—C1	−1.9 (3)
C9—C1—C6—C5	180.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.86	2.15	2.970 (2)	159
N3—H3A···O3ⁱⁱ	0.86	2.19	3.044 (2)	170
N3—H3B···N1	0.86	2.30	2.657 (2)	105
N3—H3B···O1ⁱⁱⁱ	0.86	2.59	3.019 (2)	112
N3—H3B···O2ⁱⁱⁱ	0.86	2.30	3.119 (2)	160

Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₃
M_r	223.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.2300 (7), 7.6367 (3), 15.6482 (6)
β (°)	126.234 (1)
V (Å³)	2142.76 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.975, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7933, 2115, 1389
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.01
No. of reflections	2115
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

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···O3ⁱ	0.86	2.15	2.970 (2)	159
N3—H3A···O3ⁱⁱ	0.86	2.19	3.044 (2)	170
N3—H3B···N1	0.86	2.30	2.657 (2)	105
N3—H3B···O1ⁱⁱⁱ	0.86	2.59	3.019 (2)	112
N3—H3B···O2ⁱⁱⁱ	0.86	2.30	3.119 (2)	160

Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1/2, −y+1/2, −z+1.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha. Pakistan.

References

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