2-(Hydrazonomethyl)phenol

Shang, Y.-F.; Wang, Q.-M.; Zhu, M.-L.; Zhang, Y.-H.

doi:10.1107/S1600536809045504

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3023

doi:10.1107/S1600536809045504

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2-(Hydrazonomethyl)phenol

Yan-Fang Shang,^a ^* Qing-Ming Wang,^b Miao-Li Zhu ^b and Yue-Hua Zhang ^a

^aSchool of Chemistry and Chemical Engineering, Nantong University, Nantong, JiangSu 226000, People's Republic of China, and ^bInstitute of Molecular Science, Key Laboratory of Chemical Biology and Molecular, Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: shangyanfang@ntu.edu.cn

(Received 23 October 2009; accepted 29 October 2009; online 7 November 2009)

The conformation of the title compound, C₇H₈N₂O, is stabilized by an intramolecular O—H⋯N hydrogen bond. The crystal structure shows intermolecular N—H⋯O hydrogen bonds.

Related literature

For Schiff bases as mixed-donor ligands in coordination chemistry, see: Lee et al. (2005 ). For the pharmaceutical and medicinal activity of Schiff bases, see: Sriram et al. (2006 ); Hao (2009 ); Bedia et al. (2006 ).

Experimental

Crystal data

C₇H₈N₂O
M_r = 136.15
Monoclinic, P 2₁ /c
a = 14.1010 (11) Å
b = 6.0062 (5) Å
c = 8.1979 (6) Å
β = 102.5250 (10)°
V = 677.78 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.46 × 0.45 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.959, T_max = 0.968
3351 measured reflections
1203 independent reflections
1081 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.110
S = 1.06
1203 reflections
93 parameters
.
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86	2.56	3.3076 (17)	145
N2—H2B⋯O1ⁱⁱ	0.86	2.23	3.0530 (16)	160
O1—H1⋯N1	0.82	1.89	2.6109 (15)	147
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045504/bt5112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045504/bt5112Isup2.hkl

checkCIF report

Comment top

Schiff bases are one of the most prevalent and important mixed-donor ligand in coordination chemistry (Lee et al., 2005). Recently, the synthesis, structure and properties of Schiff base complexes have stimulated much more interest for their noteworthy contributions in pharmaceutical and medicinal activity (Sriram et al., 2006; Hao 2009; Bedia et al., 2006).

The X-ray structural analysis confirmed the assignment of the structure of the title compound(I). The molecular structure is depicted in Fig. 1, and the crystal packing of the title compound(I) is depicted in Fig. 2. In the crystal structure,intermolecular N—H···O, N—H···N and intramolecular O—H···N hydrogen bonds contribute to form the title compound(I).

Related literature top

For Schiff bases as mixed-donor ligands in coordination chemistry, see: Lee et al. (2005). For the pharmaceutical and medicinal activity of Schiff bases, see: Sriram et al. (2006); Hao (2009); Bedia et al. (2006).

Experimental top

35% of hydrazine hydrate (0.50 mL, 10 mmol) and salicylidence (0.52 mL, 5 mmol) were mixed in 50.0 mL ethanol and refluxed for 3 h. When the solution was cooled to room temperature, a light yellow solid was obtained, and light yellow block shaped crystals were formed from the filtrate by slow evaporation of the solution in air after a few days. The yield of the isolated yellow solid was 0.62 g.(90%).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. A view of the title compound with displacement ellipsoids drawn at the 30% probability level. Dashed line indicates hydrogen bonding interactions.
	Fig. 2. Crystal packing of the title compound.

2-(Hydrazonomethyl)phenol top

Crystal data top

C₇H₈N₂O	F(000) = 288
M_r = 136.15	D_x = 1.334 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2298 reflections
a = 14.1010 (11) Å	θ = 3.0–28.4°
b = 6.0062 (5) Å	µ = 0.09 mm⁻¹
c = 8.1979 (6) Å	T = 296 K
β = 102.525 (1)°	Block, yellow
V = 677.78 (9) Å³	0.46 × 0.45 × 0.35 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1203 independent reflections
Radiation source: fine-focus sealed tube	1081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 25.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→16
T_min = 0.959, T_max = 0.968	k = −6→7
3351 measured reflections	l = −9→8

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)] = 0.036	w = 1/[σ²(F_o²) + (0.0587P)² + 0.1774P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.33 e Å⁻³
1203 reflections	Δρ_min = −0.29 e Å⁻³
93 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.129 (12)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₇H₈N₂O	V = 677.78 (9) Å³
M_r = 136.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.1010 (11) Å	µ = 0.09 mm⁻¹
b = 6.0062 (5) Å	T = 296 K
c = 8.1979 (6) Å	0.46 × 0.45 × 0.35 mm
β = 102.525 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1203 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1081 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.968	R_int = 0.013
3351 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	93 parameters
wR(F²) = 0.110	0 restraints
S = 1.06	Δρ_max = 0.33 e Å⁻³
1203 reflections	Δρ_min = −0.29 e Å⁻³

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
C1	0.22022 (10)	−0.1162 (2)	0.13139 (16)	0.0374 (4)
C2	0.27892 (11)	−0.2576 (3)	0.24310 (18)	0.0462 (4)
H2	0.2554	−0.3958	0.2670	0.055*
C3	0.37226 (12)	−0.1944 (3)	0.3192 (2)	0.0546 (5)
H3	0.4111	−0.2898	0.3948	0.065*
C4	0.40836 (11)	0.0097 (3)	0.2837 (2)	0.0568 (5)
H4	0.4715	0.0513	0.3339	0.068*
C5	0.34970 (11)	0.1512 (3)	0.17277 (19)	0.0487 (4)
H5	0.3743	0.2881	0.1487	0.058*
C6	0.25465 (9)	0.0945 (2)	0.09582 (16)	0.0372 (4)
C7	0.19290 (10)	0.2536 (2)	−0.01248 (16)	0.0392 (4)
H7	0.2190	0.3883	−0.0376	0.047*
N1	0.10354 (8)	0.21085 (19)	−0.07344 (14)	0.0407 (3)
N2	0.04759 (9)	0.3659 (2)	−0.17427 (15)	0.0507 (4)
H2A	0.0693	0.4889	−0.2059	0.061*
H2B	−0.0089	0.3460	−0.1530	0.061*
O1	0.12928 (7)	−0.18636 (16)	0.05811 (13)	0.0476 (3)
H1	0.0993	−0.0840	0.0039	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0428 (8)	0.0355 (7)	0.0358 (7)	−0.0005 (6)	0.0127 (6)	−0.0036 (5)
C2	0.0587 (9)	0.0381 (8)	0.0439 (8)	0.0040 (6)	0.0157 (7)	0.0026 (6)
C3	0.0576 (10)	0.0566 (10)	0.0467 (9)	0.0148 (8)	0.0050 (7)	0.0038 (7)
C4	0.0439 (8)	0.0645 (11)	0.0574 (10)	0.0009 (8)	0.0007 (7)	−0.0041 (8)
C5	0.0468 (8)	0.0447 (8)	0.0543 (9)	−0.0070 (6)	0.0106 (7)	−0.0034 (7)
C6	0.0418 (7)	0.0351 (7)	0.0363 (7)	−0.0016 (6)	0.0118 (5)	−0.0038 (5)
C7	0.0471 (8)	0.0323 (7)	0.0399 (7)	−0.0060 (6)	0.0130 (6)	0.0003 (6)
N1	0.0468 (7)	0.0364 (6)	0.0385 (6)	−0.0013 (5)	0.0083 (5)	0.0020 (5)
N2	0.0523 (8)	0.0466 (8)	0.0522 (8)	0.0037 (6)	0.0092 (6)	0.0140 (6)
O1	0.0451 (6)	0.0353 (6)	0.0607 (7)	−0.0054 (4)	0.0078 (5)	0.0039 (5)

Geometric parameters (Å, º) top

C1—O1	1.3597 (16)	C5—C6	1.3941 (19)
C1—C2	1.384 (2)	C5—H5	0.9300
C1—C6	1.409 (2)	C6—C7	1.4574 (19)
C2—C3	1.382 (2)	C7—N1	1.2768 (18)
C2—H2	0.9300	C7—H7	0.9300
C3—C4	1.382 (2)	N1—N2	1.3749 (16)
C3—H3	0.9300	N2—H2A	0.8604
C4—C5	1.381 (2)	N2—H2B	0.8604
C4—H4	0.9300	O1—H1	0.8200

O1—C1—C2	118.26 (12)	C4—C5—H5	119.1
O1—C1—C6	121.42 (12)	C6—C5—H5	119.1
C2—C1—C6	120.32 (13)	C5—C6—C1	117.79 (13)
C3—C2—C1	120.28 (14)	C5—C6—C7	120.29 (13)
C3—C2—H2	119.9	C1—C6—C7	121.88 (12)
C1—C2—H2	119.9	N1—C7—C6	121.00 (12)
C2—C3—C4	120.46 (15)	N1—C7—H7	119.5
C2—C3—H3	119.8	C6—C7—H7	119.5
C4—C3—H3	119.8	C7—N1—N2	119.21 (12)
C5—C4—C3	119.27 (15)	N1—N2—H2A	124.6
C5—C4—H4	120.4	N1—N2—H2B	102.7
C3—C4—H4	120.4	H2A—N2—H2B	125.9
C4—C5—C6	121.86 (14)	C1—O1—H1	109.5

O1—C1—C2—C3	179.29 (13)	O1—C1—C6—C5	−178.27 (12)
C6—C1—C2—C3	−0.8 (2)	C2—C1—C6—C5	1.82 (19)
C1—C2—C3—C4	−0.5 (2)	O1—C1—C6—C7	4.02 (19)
C2—C3—C4—C5	0.8 (2)	C2—C1—C6—C7	−175.89 (12)
C3—C4—C5—C6	0.3 (2)	C5—C6—C7—N1	−174.54 (13)
C4—C5—C6—C1	−1.6 (2)	C1—C6—C7—N1	3.1 (2)
C4—C5—C6—C7	176.17 (13)	C6—C7—N1—N2	179.61 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.56	3.3076 (17)	145
N2—H2B···O1ⁱⁱ	0.86	2.23	3.0530 (16)	160
O1—H1···N1	0.82	1.89	2.6109 (15)	147

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

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O
M_r	136.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.1010 (11), 6.0062 (5), 8.1979 (6)
β (°)	102.525 (1)
V (Å³)	677.78 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.46 × 0.45 × 0.35

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.959, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	3351, 1203, 1081
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.110, 1.06
No. of reflections	1203
No. of parameters	93
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.29

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.56	3.3076 (17)	145.2
N2—H2B···O1ⁱⁱ	0.86	2.23	3.0530 (16)	159.8
O1—H1···N1	0.82	1.89	2.6109 (15)	146.7

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

Acknowledgements

Y-FS acknowledges financial support from the Natural Science Foundation of Nantong University in China (grant No. 07z025).

References

Bedia, K. K., Elcin, O., Seda, U., Fatma, K., Nathaly, S., Sevim, R. & Dimoglo, A. (2006). Eur. J. Med. Chem. 41, 1253–1261. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hao, Y.-M. (2009). Acta Cryst. E65, o2600. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, B. Y., Kwon, H. Y., Lee, S. Y., Na, S. J., Han, S. I., Yun, H., Lee, H. & Park, Y. W. (2005). J. Am. Chem. Soc. 127, 3031–3037. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sriram, D., Yogeeswari, P., Myneedu, N. S. & Saraswat, V. (2006). Bioorg. Med. Chem. Lett. 16, 2127–2129. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar