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

Abstract

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 = 14.3101 (4) Å

• b = 9.3620 (2) Å

• c = 10.2697 (2) Å

• V = 1375.84 (6) ų

• 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[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811053268/hb6561Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H = 0.95 Å, U_iso(H) = 1.2 U_eq(C)] and were included in the refinement in the riding model approximation. The hydroxyl and amino H-atoms were refined freely. In the absence of significant anomalous scattering effects, 242 Friedel pairs were averaged in the final refinement.

Figures

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.

Crystal data

C15H14N4O3	F(000) = 624
Mr = 298.30	Dx = 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

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	Rint = 0.014
Detector resolution: 10.4041 pixels mm-1	θmax = 76.7°, θmin = 6.2°
ω scan	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→10
Tmin = 0.342, Tmax = 1.000	l = −10→12
2323 measured reflections

Refinement

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(Fo2) + (0.0579P)2 + 0.2173P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
757 reflections	Δρmax = 0.16 e Å−3
110 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, z.

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···O2ii	0.89 (3)	2.12 (3)	2.983 (2)	161 (2)

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