2-[((E)-2-{2-[(E)-2-Hy­droxy­benzyl­idene]hydrazinecarbon­yl}hydrazinyl­idene)meth­yl]phenol

Bikas, R.; Anarjan, P.M.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811053268

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o193

doi:10.1107/S1600536811053268

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2-[((E)-2-{2-[(E)-2-Hydroxybenzylidene]hydrazinecarbonyl}hydrazinylidene)methyl]phenol

Rahman Bikas,^a ‡ Parisa Mahboubi Anarjan,^b Seik Weng Ng ^c,^d and Edward R. T. Tiekink ^c ^*

^aYoung Researchers Club, Tabriz Branch, Islamic Azad University, Tabriz, Iran, ^bDepartment of Chemistry, University of Zanjan 45195-313, Zanjan, Iran, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 9 December 2011; accepted 10 December 2011; online 21 December 2011)

The molecule of the title compound, C₁₅H₁₄N₄O₃, is completed by the application of crystallographic twofold symmetry, with the carbonyl group lying on the rotation axis. The molecule is close to planar: the greatest deviation of a torsion angle from 0° is 7.3 (2)° about the bond linking the phenol ring to the rest of the molecule. An intramolecular O—H⋯N(imine) hydrogen bond is formed in each half of the molecule. The carbonyl O atom is anti with respect to the amine H atoms and this allows for the formation of N—H⋯O(hydroxyl) hydrogen bonds in the crystal, which results in supramolecular layers lying parallel to (100).

Related literature

For the structures of related carbohydrazides, see: Bikas et al. (2010a ,b ).

Experimental

Crystal data

C₁₅H₁₄N₄O₃
M_r = 298.30
Orthorhombic, A b a 2
a = 14.3101 (4) Å
b = 9.3620 (2) Å
c = 10.2697 (2) Å
V = 1375.84 (6) Å³
Z = 4
Cu Kα radiation
μ = 0.86 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.342, T_max = 1.000
2323 measured reflections
757 independent reflections
750 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.075
S = 1.10
757 reflections
110 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N2	0.86 (3)	1.79 (4)	2.5710 (17)	150 (3)
N1—H1⋯O2ⁱ	0.89 (3)	2.12 (3)	2.983 (2)	161 (2)
Symmetry code: (i) $[-x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053268/hb6561sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053268/hb6561Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053268/hb6561Isup3.cml

checkCIF report

Comment top

In connection with previous structural studies of carbohydrazide derivatives (Bikas et al., 2010a,b), the title compound, (I), was investigated. The molecule, Fig. 1, has crystallographic twofold symmetry. The molecule is essentially planar with a r.m.s. deviation for all 22 atoms comprising the full molecule being 0.074 Å. The maximum deviation from 0° for a torsion angle in the molecule is 7.3 (2)° for N2—C2—C3—C8. The carbonyl-O atom is anti with respect to the amine-H atoms, and the conformation about the C2═N2 imine bond [1.2857 (19) Å] is E.The hydroxyl-H atom forms an intramolecular hydrogen bond to the imine-H atom, Table 1.

In the crystal, the amine-H atoms form hydrogen bonds to the hydroxyl-O atoms to form supramolecular layers parallel to (100), Fig. 2 and Table 1.

Related literature top

For the structures of related carbohydrazides, see: Bikas et al. (2010a,b).

Experimental top

All reagents were commercially available and used as received. A methanol (10 ml) solution of 2-hydroxybenzaldehyde (3 mmol) was added drop-wise to a methanol solution (10 ml) of carbohydrazide (1.5 mmol), and the mixture was refluxed for 3 h. Then the solution was evaporated on a steam bath to 5 ml and cooled to room temperature. White precipitates of the title compound were separated and filtered off, washed with cooled methanol (3 ml) and then dried in air. Crystals of the title compound were obtained from its methanol solution by slow solvent evaporation. Yield: 94%. M.pt. 496–497 K. Selected IR data (cm^-1): 3272 (v. broad, N—H), 1721 (C═O); 1625 (s, C═N(azomethine)); 959 (m, N—N); 1353, 1273 (s, C—O).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of (I) showing displacement ellipsoids at the 70% probability level. The molecule has twofold symmetry and the unlabelled atoms are related by the symmetry operation 1 - x, 1 - y, z.
	Fig. 2. A view of the supramolecular layer parallel to (100) in (I). The N—H···O hydrogen bonds are shown as blue dashed lines.

2-[((E)-2-{2-[(E)-2- Hydroxybenzylidene]hydrazinecarbonyl}hydrazinylidene)methyl]phenol top

Crystal data top

C₁₅H₁₄N₄O₃	F(000) = 624
M_r = 298.30	D_x = 1.440 Mg m⁻³
Orthorhombic, Aba2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: A 2 -2ac	Cell parameters from 1858 reflections
a = 14.3101 (4) Å	θ = 3.1–76.5°
b = 9.3620 (2) Å	µ = 0.86 mm⁻¹
c = 10.2697 (2) Å	T = 100 K
V = 1375.84 (6) Å³	Prism, colourless
Z = 4	0.25 × 0.25 × 0.10 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	757 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	750 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.014
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.7°, θ_min = 6.2°
ω scan	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→10
T_min = 0.342, T_max = 1.000	l = −10→12
2323 measured reflections

Refinement top

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0579P)² + 0.2173P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
757 reflections	Δρ_max = 0.16 e Å⁻³
110 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (7)

Crystal data top

C₁₅H₁₄N₄O₃	V = 1375.84 (6) Å³
M_r = 298.30	Z = 4
Orthorhombic, Aba2	Cu Kα radiation
a = 14.3101 (4) Å	µ = 0.86 mm⁻¹
b = 9.3620 (2) Å	T = 100 K
c = 10.2697 (2) Å	0.25 × 0.25 × 0.10 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	757 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	750 reflections with I > 2σ(I)
T_min = 0.342, T_max = 1.000	R_int = 0.014
2323 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	1 restraint
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.16 e Å⁻³
757 reflections	Δρ_min = −0.21 e Å⁻³
110 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
O1	0.5000	0.5000	0.50067 (16)	0.0218 (4)
O2	0.59665 (8)	0.87891 (12)	0.43307 (12)	0.0197 (3)
N1	0.52439 (9)	0.61383 (13)	0.69670 (15)	0.0186 (3)
N2	0.55917 (9)	0.73346 (13)	0.63891 (13)	0.0170 (3)
C1	0.5000	0.5000	0.6191 (2)	0.0174 (4)
C2	0.57681 (11)	0.84255 (16)	0.71089 (15)	0.0172 (3)
H2A	0.5646	0.8395	0.8018	0.021*
C3	0.61574 (10)	0.97076 (15)	0.65176 (15)	0.0159 (4)
C4	0.64432 (11)	1.08454 (17)	0.73122 (16)	0.0191 (4)
H4	0.6380	1.0769	0.8230	0.023*
C5	0.68171 (11)	1.20828 (18)	0.67764 (18)	0.0211 (4)
H5	0.7009	1.2847	0.7324	0.025*
C6	0.69086 (11)	1.21928 (18)	0.54321 (19)	0.0219 (4)
H6	0.7165	1.3036	0.5062	0.026*
C7	0.66290 (11)	1.10842 (16)	0.46270 (15)	0.0195 (4)
H7	0.6698	1.1169	0.3710	0.023*
C8	0.62482 (9)	0.98474 (16)	0.51579 (14)	0.0159 (4)
H1	0.5006 (17)	0.614 (2)	0.777 (3)	0.023 (5)*
H2	0.579 (2)	0.809 (3)	0.481 (3)	0.051 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0307 (8)	0.0208 (7)	0.0138 (8)	−0.0031 (6)	0.000	0.000
O2	0.0260 (6)	0.0186 (5)	0.0146 (5)	−0.0020 (4)	−0.0006 (5)	−0.0009 (4)
N1	0.0253 (7)	0.0169 (7)	0.0136 (6)	−0.0027 (5)	0.0024 (5)	0.0014 (5)
N2	0.0183 (6)	0.0166 (7)	0.0160 (7)	0.0001 (5)	−0.0004 (5)	0.0014 (5)
C1	0.0181 (10)	0.0175 (10)	0.0167 (10)	0.0017 (7)	0.000	0.000
C2	0.0176 (6)	0.0190 (7)	0.0149 (7)	0.0010 (5)	−0.0001 (5)	0.0002 (6)
C3	0.0147 (7)	0.0180 (7)	0.0150 (7)	0.0022 (6)	−0.0004 (6)	0.0005 (6)
C4	0.0181 (7)	0.0219 (8)	0.0174 (8)	0.0007 (6)	−0.0004 (6)	−0.0010 (7)
C5	0.0195 (7)	0.0197 (8)	0.0241 (8)	−0.0025 (5)	0.0002 (6)	−0.0040 (6)
C6	0.0186 (8)	0.0209 (8)	0.0261 (9)	−0.0031 (5)	0.0009 (7)	0.0035 (7)
C7	0.0190 (7)	0.0230 (7)	0.0166 (8)	−0.0003 (6)	0.0009 (6)	0.0027 (6)
C8	0.0136 (7)	0.0181 (7)	0.0161 (9)	0.0016 (5)	−0.0009 (6)	−0.0003 (6)

Geometric parameters (Å, º) top

O1—C1	1.217 (3)	C3—C4	1.403 (2)
O2—C8	1.3660 (19)	C3—C8	1.408 (2)
O2—H2	0.86 (3)	C4—C5	1.390 (2)
N1—N2	1.3617 (16)	C4—H4	0.9500
N1—C1	1.3754 (19)	C5—C6	1.391 (3)
N1—H1	0.89 (3)	C5—H5	0.9500
N2—C2	1.2857 (19)	C6—C7	1.386 (2)
C1—N1ⁱ	1.3754 (19)	C6—H6	0.9500
C2—C3	1.456 (2)	C7—C8	1.391 (2)
C2—H2A	0.9500	C7—H7	0.9500

C8—O2—H2	106 (2)	C5—C4—H4	119.5
N2—N1—C1	118.53 (14)	C3—C4—H4	119.5
N2—N1—H1	122.6 (13)	C4—C5—C6	119.41 (17)
C1—N1—H1	116.2 (14)	C4—C5—H5	120.3
C2—N2—N1	118.33 (13)	C6—C5—H5	120.3
O1—C1—N1	125.38 (10)	C7—C6—C5	120.64 (16)
O1—C1—N1ⁱ	125.38 (10)	C7—C6—H6	119.7
N1—C1—N1ⁱ	109.2 (2)	C5—C6—H6	119.7
N2—C2—C3	119.35 (14)	C6—C7—C8	120.17 (15)
N2—C2—H2A	120.3	C6—C7—H7	119.9
C3—C2—H2A	120.3	C8—C7—H7	119.9
C4—C3—C8	118.64 (14)	O2—C8—C7	118.40 (14)
C4—C3—C2	119.67 (14)	O2—C8—C3	121.46 (14)
C8—C3—C2	121.69 (14)	C7—C8—C3	120.14 (14)
C5—C4—C3	120.99 (16)

C1—N1—N2—C2	176.05 (12)	C4—C5—C6—C7	0.1 (2)
N2—N1—C1—O1	−5.97 (14)	C5—C6—C7—C8	0.3 (2)
N2—N1—C1—N1ⁱ	174.03 (14)	C6—C7—C8—O2	178.90 (13)
N1—N2—C2—C3	178.82 (12)	C6—C7—C8—C3	−0.9 (2)
N2—C2—C3—C4	−173.31 (13)	C4—C3—C8—O2	−178.76 (13)
N2—C2—C3—C8	7.3 (2)	C2—C3—C8—O2	0.6 (2)
C8—C3—C4—C5	−0.6 (2)	C4—C3—C8—C7	1.1 (2)
C2—C3—C4—C5	−179.99 (13)	C2—C3—C8—C7	−179.58 (13)
C3—C4—C5—C6	0.0 (2)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2	0.86 (3)	1.79 (4)	2.5710 (17)	150 (3)
N1—H1···O2ⁱⁱ	0.89 (3)	2.12 (3)	2.983 (2)	161 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₄O₃
M_r	298.30
Crystal system, space group	Orthorhombic, Aba2
Temperature (K)	100
a, b, c (Å)	14.3101 (4), 9.3620 (2), 10.2697 (2)
V (Å³)	1375.84 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.25 × 0.25 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.342, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2323, 757, 750
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.075, 1.10
No. of reflections	757
No. of parameters	110
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2	0.86 (3)	1.79 (4)	2.5710 (17)	150 (3)
N1—H1···O2ⁱ	0.89 (3)	2.12 (3)	2.983 (2)	161 (2)

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

Footnotes

‡Additional correspondence author, e-mail: bikas_r@yahoo.com.

Acknowledgements

The authors are grateful to the Islamic Azad University (Tabriz Branch), the University of Zanjan and the University of Malaya for support of this study.

References

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