1,5-Bis(2-hy­droxy-3-meth­oxy­benzyl­idene)carbonohydrazide methanol 0.47-solvate

Sow, M.M.; Diouf, O.; Seck, M.; Barry, A.H.; Gaye, M.

doi:10.1107/S1600536814004802

organic compounds

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doi:10.1107/S1600536814004802

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1,5-Bis(2-hydroxy-3-methoxybenzylidene)carbonohydrazide methanol 0.47-solvate

Mouhamadou Moustapha Sow,^a Ousmane Diouf,^a Matar Seck,^b Aliou Hamady Barry ^c and Mohamed Gaye ^a ^*

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bDépartement de Chimie, Faculté de Medecine, de Pharmacie et d'Odonto-stomatologie, Université Cheikh Anta Diop, Dakar, Senegal, and ^cDépartement de Chimie, Faculté des Sciences et Techniques, Université de Nouakchott, Mauritania
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 11 February 2014; accepted 2 March 2014; online 12 March 2014)

In the title compound, C₁₇H₁₈N₄O₅·0.47CH₃OH, the virtually planar (r.m.s. deviation = 0.128 Å) carbonohydrazide molecule is located on a twofold axis and conformation of its C=N bonds is E. There are short intramolecular O—H⋯N hydrogen bonds between the hydroxy groups and hydrazide N atoms. In the crystal, bifurcated N—H⋯(O,O) hydrogen bonds assemble the carbonohydrazide molecules into a three-dimensional network. There are C₂ symmetric voids in this network, 47% of which are occupied by disordered methanol molecules.

CCDC reference: 989432

Related literature

For related structures, see: Du & Zhang (2010 ); He et al. (2010 ); Kong et al. (2010 ). For the biological activity of carbonohydrazides, see: Bacchi et al. (1999 ); El-Gammal et al. (2012 ).

Experimental

Crystal data

C₁₇H₁₈N₄O₅·0.47CH₄O
M_r = 373.40
Orthorhombic, F d d 2
a = 9.4470 (7) Å
b = 17.5850 (9) Å
c = 22.8714 (12) Å
V = 3799.5 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.1 × 0.08 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
9573 measured reflections
862 independent reflections
658 reflections with I > 2σ(I)
R_int = 0.105
2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.111
S = 1.25
862 reflections
146 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.91 (5)	1.86 (5)	2.703 (5)	152 (5)
N2—H2N⋯O3ⁱ	0.94 (6)	2.38 (5)	3.044 (6)	128 (4)
N2—H2N⋯O1ⁱ	0.94 (6)	2.33 (6)	3.204 (6)	155 (4)
Symmetry code: (i) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 989432

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814004802/gk2603sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004802/gk2603Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814004802/gk2603Isup3.cml

checkCIF report

Comment top

Carbonohydrazide derivatives give rise to a large spectrum of biological properties such as antioxidant (El-Gammal et al., 2012) and anticancer activities (Bacchi et al., 1999). We report here the crystal structure of the title compound synthesized according to literature (He et al., 2010; Du et al., 2010). All parameters are within normal ranges and comparable with the related structures (Kong et al., 2010).

The molecular structure of the title compound is shown in Fig. 1. The complete carbonohydrazide molecule is generated by a twofold crystallographic axis passing throuth the atoms C8 and O2. A three-center O···(N)H···O intermolecular hydrogen bond involving the amido H atoms and the phenoxo and methoxy O atoms is observed (Fig. 2). There are voids in a three dimensional network containing solvent methanol molecules. Only one methanol molecule can be accommodated in a small void that has C₂ symmetry. This leads to disorder of methanol molecules. In addition refinement of occupancy factors of methanol O and C atoms converged at 0.234 (1), indicating that 47% of voids are occupied by the solvent.

Related literature top

For related structures, see: Du & Zhang (2010); He et al. (2010); Kong et al. (2010). For the biological activity of carbonohydrazides, see: Bacchi et al. (1999); El-Gammal et al. (2012).

Experimental top

In a round bottomed flask, carbonohydrazide (1.0 g, 11.11 mmol) was introduced with methanol (10 ml). o-Vanillin (3.3 g, 22.22 mmol) dissolved in 10 ml of the same solvent was added. Two drops of glacial acetic acid were added while stirring. After one hour under reflux, the precipitate formed that after cooling to room temperature was filtered off and washed with cold methanol. The resulting solid was dried in air. The filtrate was left at room temperature. Slow evaporation of the solvent gave colorless crystals after one day. Yield: 95%; m.p. 378 K. Anal. Calc. for [C₁₇H₁₈N₄O₅] (%): C, 56.98; H, 5.06, N, 15.63. Found: C, 56.96; H, 5.04; N, 15.60. Selected IR data (cm^-1, KBr pellet): 3291, 2942, 1696, 1553, 1200, 1167. ¹H-NMR (DMSO-d6) δ: 3.8 (s, 6H, O—CH3); 6.7 – 7.1 (m, 6H, H_Aromatic); 8.5 (s, 2H, H—C═N); 7.3 (s, 1H, H—N); 11 (s, 2H, H—O) p.p.m. ¹³C-NMR (DMSO-d₆) d: 151.8 (C═O); 147.8, 146.1, 119.5, 119.4, 118.8, 112.8 (C_Aromatic); 58,7 (–O—CH₃).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level. Only one position of the disordered solvent methanol molecule is shown for clarity. The symmetry code for generating primed atoms is 2-x,-y,z
	Fig. 2. Intramoleculr and intermolecular hydrogen bonds. Solvent methanol molecules are omitted as they do not form hydrogen bonds.

1,5-Bis(2-hydroxy-3-methoxybenzylidene)carbonohydrazide methanol 0.47-solvate top

Crystal data top

C₁₇H₁₈N₄O₅·0.47CH₄O	F(000) = 1571.4
M_r = 373.40	D_x = 1.306 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 25 reflections
a = 9.4470 (7) Å	θ = 11–15°
b = 17.5850 (9) Å	µ = 0.10 mm⁻¹
c = 22.8714 (12) Å	T = 293 K
V = 3799.5 (4) Å³	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.105
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.6°
Graphite monochromator	h = −11→11
non–profiled ω/2θ scans	k = −1→20
9573 measured reflections	l = −27→27
862 independent reflections	2 standard reflections every 120 min
658 reflections with I > 2σ(I)	intensity decay: 2%

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) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ²(F_o²) + (0.0306P)² + 5.2614P] where P = (F_o² + 2F_c²)/3
862 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₇H₁₈N₄O₅·0.47CH₄O	V = 3799.5 (4) Å³
M_r = 373.40	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 9.4470 (7) Å	µ = 0.10 mm⁻¹
b = 17.5850 (9) Å	T = 293 K
c = 22.8714 (12) Å	0.1 × 0.08 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.105
9573 measured reflections	2 standard reflections every 120 min
862 independent reflections	intensity decay: 2%
658 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	Δρ_max = 0.17 e Å⁻³
862 reflections	Δρ_min = −0.19 e Å⁻³
146 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.6805 (4)	0.1635 (2)	0.02775 (15)	0.0559 (10)
O2	1.0000	0.0000	0.0525 (2)	0.0641 (14)
O3	0.4920 (4)	0.2637 (2)	−0.00424 (17)	0.0680 (12)
N1	0.8123 (4)	0.0896 (2)	0.11591 (18)	0.0471 (10)
N2	0.9127 (5)	0.0436 (2)	0.1418 (2)	0.0533 (11)
C1	0.6048 (5)	0.1974 (3)	0.0728 (2)	0.0459 (12)
C2	0.5016 (5)	0.2512 (3)	0.0560 (2)	0.0512 (13)
C3	0.4200 (5)	0.2864 (3)	0.0996 (3)	0.0567 (14)
H3	0.3505	0.3211	0.0888	0.068*
C4	0.4409 (5)	0.2704 (3)	0.1594 (3)	0.0595 (15)
H4	0.3856	0.2946	0.1874	0.071*
C5	0.5434 (5)	0.2189 (3)	0.1765 (2)	0.0528 (13)
H5	0.5580	0.2087	0.2159	0.063*
C6	0.6269 (5)	0.1813 (3)	0.1329 (2)	0.0423 (11)
C7	0.7364 (5)	0.1284 (3)	0.1531 (2)	0.0459 (12)
H7	0.7519	0.1223	0.1930	0.055*
C8	1.0000	0.0000	0.1068 (3)	0.0467 (17)
C9	0.4052 (7)	0.3261 (4)	−0.0244 (3)	0.0779 (19)
H9A	0.4081	0.3283	−0.0663	0.117*
H9B	0.4405	0.3729	−0.0086	0.117*
H9C	0.3093	0.3185	−0.0118	0.117*
O4	0.579 (2)	0.1913 (12)	0.3182 (9)	0.098 (9)	0.234 (11)
H1M	0.5601	0.1599	0.3453	0.148*	0.234 (11)
C10	0.703 (3)	0.2337 (18)	0.3207 (10)	0.075 (10)	0.234 (11)
H10A	0.7221	0.2638	0.3554	0.113*	0.234 (11)
H10B	0.7221	0.2638	0.2861	0.113*	0.234 (11)
H10C	0.7632	0.1890	0.3207	0.113*	0.234 (11)
H1O	0.743 (5)	0.134 (3)	0.048 (2)	0.057 (15)*
H2N	0.916 (5)	0.040 (3)	0.183 (3)	0.052 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.062 (2)	0.055 (2)	0.051 (2)	0.0187 (18)	−0.0048 (18)	−0.0067 (17)
O2	0.077 (4)	0.069 (3)	0.047 (3)	0.019 (3)	0.000	0.000
O3	0.076 (3)	0.063 (2)	0.066 (3)	0.026 (2)	−0.0196 (19)	−0.001 (2)
N1	0.043 (2)	0.045 (2)	0.053 (2)	0.004 (2)	−0.0026 (19)	0.0038 (19)
N2	0.054 (3)	0.059 (2)	0.047 (3)	0.020 (2)	−0.001 (2)	0.004 (2)
C1	0.038 (3)	0.044 (2)	0.056 (3)	0.000 (2)	−0.002 (2)	−0.005 (2)
C2	0.046 (3)	0.042 (2)	0.065 (3)	0.004 (2)	−0.010 (3)	0.001 (3)
C3	0.039 (3)	0.049 (3)	0.082 (4)	0.006 (2)	−0.001 (3)	−0.005 (3)
C4	0.047 (3)	0.052 (3)	0.080 (4)	0.002 (3)	0.017 (3)	−0.008 (3)
C5	0.046 (3)	0.053 (3)	0.059 (3)	−0.002 (2)	0.014 (2)	0.002 (3)
C6	0.039 (3)	0.035 (2)	0.052 (3)	−0.001 (2)	0.004 (2)	−0.002 (2)
C7	0.047 (3)	0.044 (3)	0.046 (3)	−0.001 (2)	0.000 (2)	0.006 (2)
C8	0.047 (4)	0.040 (4)	0.053 (5)	0.003 (3)	0.000	0.000
C9	0.082 (4)	0.058 (3)	0.094 (5)	0.015 (3)	−0.025 (4)	0.014 (3)
O4	0.117 (19)	0.087 (15)	0.091 (17)	0.004 (12)	0.030 (13)	0.010 (12)
C10	0.07 (2)	0.10 (3)	0.057 (16)	0.021 (19)	−0.001 (11)	−0.018 (15)

Geometric parameters (Å, º) top

O1—C1	1.389 (6)	C4—H4	0.9300
O1—H1O	0.91 (5)	C5—C6	1.433 (7)
O2—C8	1.243 (8)	C5—H5	0.9300
O3—C2	1.397 (6)	C6—C7	1.466 (6)
O3—C9	1.445 (6)	C7—H7	0.9300
N1—C7	1.305 (6)	C8—N2ⁱ	1.381 (6)
N1—N2	1.381 (5)	C9—H9A	0.9600
N2—C8	1.381 (6)	C9—H9B	0.9600
N2—H2N	0.94 (6)	C9—H9C	0.9600
C1—C2	1.413 (6)	O4—C10	1.39 (3)
C1—C6	1.418 (7)	O4—H1M	0.8500
C2—C3	1.405 (8)	C10—C10ⁱⁱ	1.06 (5)
C3—C4	1.411 (8)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.382 (7)	C10—H10C	0.9700

C1—O1—H1O	102 (3)	N1—C7—C6	121.0 (4)
C2—O3—C9	118.1 (4)	N1—C7—H7	119.5
C7—N1—N2	113.9 (4)	C6—C7—H7	119.5
N1—N2—C8	119.1 (5)	O2—C8—N2	125.4 (3)
N1—N2—H2N	120 (3)	O2—C8—N2ⁱ	125.4 (3)
C8—N2—H2N	121 (3)	N2—C8—N2ⁱ	109.2 (7)
O1—C1—C2	116.1 (5)	O3—C9—H9A	109.5
O1—C1—C6	123.9 (4)	O3—C9—H9B	109.5
C2—C1—C6	120.0 (5)	H9A—C9—H9B	109.5
O3—C2—C3	126.5 (5)	O3—C9—H9C	109.5
O3—C2—C1	114.8 (5)	H9A—C9—H9C	109.5
C3—C2—C1	118.7 (5)	H9B—C9—H9C	109.5
C2—C3—C4	121.7 (5)	C10—O4—H1M	119.9
C2—C3—H3	119.2	C10ⁱⁱ—C10—O4	177.6 (17)
C4—C3—H3	119.2	C10ⁱⁱ—C10—H10A	63.1
C5—C4—C3	120.2 (5)	O4—C10—H10A	118.9
C5—C4—H4	119.9	C10ⁱⁱ—C10—H10B	63.1
C3—C4—H4	119.9	O4—C10—H10B	114.5
C4—C5—C6	119.4 (5)	H10A—C10—H10B	109.6
C4—C5—H5	120.3	C10ⁱⁱ—C10—H10C	87.1
C6—C5—H5	120.3	O4—C10—H10C	93.3
C1—C6—C5	120.1 (4)	H10A—C10—H10C	109.6
C1—C6—C7	122.3 (4)	H10B—C10—H10C	109.6
C5—C6—C7	117.5 (4)

Symmetry codes: (i) −x+2, −y, z; (ii) −x+3/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.91 (5)	1.86 (5)	2.703 (5)	152 (5)
N2—H2N···O3ⁱⁱⁱ	0.94 (6)	2.38 (5)	3.044 (6)	128 (4)
N2—H2N···O1ⁱⁱⁱ	0.94 (6)	2.33 (6)	3.204 (6)	155 (4)

Symmetry code: (iii) x+1/4, −y+1/4, z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.91 (5)	1.86 (5)	2.703 (5)	152 (5)
N2—H2N···O3ⁱ	0.94 (6)	2.38 (5)	3.044 (6)	128 (4)
N2—H2N···O1ⁱ	0.94 (6)	2.33 (6)	3.204 (6)	155 (4)

Symmetry code: (i) x+1/4, −y+1/4, z+1/4.

References

Bacchi, A., Carcelli, M., Pelagatti, P., Pelizzi, C., Pelizzi, G. & Zani, F. (1999). J. Inorg. Biochem. 75, 123–133. Web of Science CrossRef PubMed CAS Google Scholar
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El-Gammal, O. A., Abu El-Reash, G. M., Ghazy, S. E. & Radwan, A. H. (2012). J. Mol. Struct. 1020, 6–15. CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,5-Bis(2-hy­dr­oxy-3-meth­­oxy­benzyl­­idene)carbonohydrazide methanol 0.47-solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

1,5-Bis(2-hydroxy-3-methoxybenzylidene)carbonohydrazide methanol 0.47-solvate