2-{[2-(4-Chloro­phen­yl)hydrazinyl­idene]meth­yl}phenol

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536811017958

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1452

doi:10.1107/S1600536811017958

Open

access

2-{[2-(4-Chlorophenyl)hydrazinylidene]methyl}phenol

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 May 2011; accepted 12 May 2011; online 20 May 2011)

In the title Schiff base molecule, C₁₃H₁₁ClN₂O, the non-H atoms are approximately coplanar (r.m.s. deviation = 0.115 Å) and the two benzene rings are twisted by 9.36 (3)° with respect to each other. The hydroxy group is hydrogen bonded to the azomethine N atom. In the crystal, an N—H⋯π interaction is observed between the imino group and the hydroxybenzene ring of an adjacent molecule.

Related literature

For the synthesis of the compound, see: Auwers (1909 ).

Experimental

Crystal data

C₁₃H₁₁ClN₂O
M_r = 246.69
Orthorhombic, P b c a
a = 10.7590 (1) Å
b = 7.3189 (1) Å
c = 28.9222 (3) Å
V = 2277.45 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.925, T_max = 0.954
20107 measured reflections
2614 independent reflections
2326 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.04
2614 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84 (2)	1.88 (2)	2.6382 (13)	149.8 (19)
N2—H2⋯Cg1ⁱ	0.859 (18)	2.73 (2)	3.3675 (12)	132.3 (17)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017958/xu5209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017958/xu5209Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811017958/xu5209Isup3.cml

checkCIF report

Comment top

There in a enormous amount of literature on Schiff bases, which are synthesized by reaction of a primary amine with a carbonyl function. The synthesis of the title hydrazone (Scheme I) was reported a century ago (Auwers, 1909). The C₁₃H₁₁ClN₂O molecule (Scheme I) is twisted along the –CH═N–NH– portion that connects the two aromatic rings. The non-hydrogen atoms approximately lie on plane (r.m.s. deviation 0.115 Å), the rings being twisted by 9.36 (3)°. The hydroxy group is hydrogen-bond donor the the azomethine N atom (Fig. 1). The amino H atom is involved in the N—H···π interaction in the crystal structure (Table 1).

Related literature top

For the synthesis of the compound, see: Auwers (1909).

Experimental top

Salicylaldehyde (1 ml, 10 mmol) and 4-chlorophenylhydrazine hydrochloride (1.8 g, 10 mmol) were dissolved in ethanol (100 ml). No HCl-abstracting reagent was added. The solution was heated for an hour. Slow evaporation of the solvent gave colorless crystals of the Schiff base.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₃H₁₁ClN₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-{[2-(4-Chlorophenyl)hydrazinylidene]methyl}phenol top

Crystal data top

C₁₃H₁₁ClN₂O	F(000) = 1024
M_r = 246.69	D_x = 1.439 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7363 reflections
a = 10.7590 (1) Å	θ = 2.4–28.3°
b = 7.3189 (1) Å	µ = 0.32 mm⁻¹
c = 28.9222 (3) Å	T = 100 K
V = 2277.45 (4) Å³	Block, colorless
Z = 8	0.25 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEX diffractometer	2614 independent reflections
Radiation source: fine-focus sealed tube	2326 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.925, T_max = 0.954	k = −9→9
20107 measured reflections	l = −37→37

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0487P)² + 0.9769P] where P = (F_o² + 2F_c²)/3
2614 reflections	(Δ/σ)_max = 0.001
162 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₁ClN₂O	V = 2277.45 (4) Å³
M_r = 246.69	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.7590 (1) Å	µ = 0.32 mm⁻¹
b = 7.3189 (1) Å	T = 100 K
c = 28.9222 (3) Å	0.25 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEX diffractometer	2614 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2326 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.954	R_int = 0.033
20107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.37 e Å⁻³
2614 reflections	Δρ_min = −0.19 e Å⁻³
162 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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.72028 (3)	0.56809 (4)	0.484943 (10)	0.02413 (12)
O1	0.75260 (9)	0.62244 (14)	0.75810 (3)	0.0202 (2)
N1	0.57723 (9)	0.76810 (14)	0.70608 (3)	0.0160 (2)
N2	0.52407 (10)	0.81449 (15)	0.66514 (4)	0.0192 (2)
C1	0.68256 (11)	0.67666 (16)	0.79476 (4)	0.0158 (2)
C2	0.72583 (11)	0.63711 (18)	0.83900 (4)	0.0183 (3)
H2A	0.8022	0.5739	0.8429	0.022*
C3	0.65750 (12)	0.68996 (16)	0.87755 (4)	0.0197 (3)
H3	0.6883	0.6646	0.9077	0.024*
C4	0.54397 (12)	0.77994 (17)	0.87237 (4)	0.0198 (3)
H4	0.4971	0.8152	0.8987	0.024*
C5	0.50049 (12)	0.81715 (16)	0.82826 (4)	0.0174 (2)
H5	0.4230	0.8778	0.8247	0.021*
C6	0.56790 (11)	0.76755 (16)	0.78874 (4)	0.0150 (2)
C7	0.51856 (11)	0.81180 (16)	0.74331 (4)	0.0157 (2)
H7	0.4414	0.8743	0.7410	0.019*
C8	0.57272 (11)	0.75285 (16)	0.62353 (4)	0.0157 (2)
C9	0.50203 (11)	0.77689 (17)	0.58344 (4)	0.0183 (3)
H9	0.4223	0.8322	0.5854	0.022*
C10	0.54686 (12)	0.72102 (17)	0.54082 (4)	0.0193 (3)
H10	0.4986	0.7382	0.5137	0.023*
C11	0.66308 (12)	0.63963 (17)	0.53830 (4)	0.0180 (2)
C12	0.73438 (12)	0.61342 (17)	0.57764 (4)	0.0182 (3)
H12	0.8137	0.5569	0.5754	0.022*
C13	0.68960 (11)	0.66998 (16)	0.62040 (4)	0.0171 (2)
H13	0.7383	0.6524	0.6474	0.020*
H1	0.7170 (18)	0.662 (3)	0.7343 (7)	0.047 (6)*
H2	0.4532 (17)	0.868 (3)	0.6662 (6)	0.032 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0330 (2)	0.02229 (18)	0.01713 (17)	0.00084 (13)	0.00504 (12)	−0.00208 (11)
O1	0.0173 (4)	0.0242 (5)	0.0191 (5)	0.0049 (4)	0.0013 (4)	−0.0008 (4)
N1	0.0172 (5)	0.0153 (5)	0.0154 (5)	−0.0010 (4)	−0.0023 (4)	0.0006 (4)
N2	0.0184 (5)	0.0240 (6)	0.0152 (5)	0.0063 (4)	−0.0014 (4)	0.0001 (4)
C1	0.0158 (6)	0.0126 (5)	0.0189 (6)	−0.0020 (4)	0.0007 (4)	−0.0014 (4)
C2	0.0186 (6)	0.0145 (6)	0.0218 (6)	−0.0009 (5)	−0.0036 (5)	0.0005 (5)
C3	0.0260 (6)	0.0158 (6)	0.0171 (6)	−0.0041 (5)	−0.0036 (5)	0.0014 (4)
C4	0.0250 (6)	0.0177 (6)	0.0166 (6)	−0.0040 (5)	0.0034 (5)	−0.0009 (5)
C5	0.0172 (6)	0.0143 (5)	0.0208 (6)	−0.0004 (5)	0.0026 (5)	−0.0005 (4)
C6	0.0155 (5)	0.0121 (5)	0.0174 (6)	−0.0022 (4)	−0.0004 (4)	0.0000 (4)
C7	0.0141 (6)	0.0133 (5)	0.0195 (6)	−0.0001 (4)	0.0002 (4)	0.0005 (4)
C8	0.0170 (6)	0.0139 (5)	0.0162 (6)	−0.0025 (4)	0.0007 (4)	0.0012 (4)
C9	0.0166 (6)	0.0185 (6)	0.0199 (6)	0.0001 (5)	−0.0021 (5)	0.0012 (5)
C10	0.0217 (6)	0.0194 (6)	0.0169 (6)	−0.0022 (5)	−0.0033 (5)	0.0010 (5)
C11	0.0241 (6)	0.0152 (5)	0.0147 (5)	−0.0024 (5)	0.0038 (5)	−0.0010 (4)
C12	0.0185 (6)	0.0153 (6)	0.0210 (6)	0.0008 (5)	0.0024 (5)	0.0024 (5)
C13	0.0175 (6)	0.0167 (6)	0.0171 (6)	−0.0006 (5)	−0.0016 (4)	0.0022 (4)

Geometric parameters (Å, º) top

Cl1—C11	1.7418 (12)	C5—C6	1.4014 (16)
O1—C1	1.3600 (15)	C5—H5	0.9500
O1—H1	0.84 (2)	C6—C7	1.4539 (16)
N1—C7	1.2883 (15)	C7—H7	0.9500
N1—N2	1.3580 (14)	C8—C9	1.3978 (16)
N2—C8	1.3878 (15)	C8—C13	1.3991 (17)
N2—H2	0.859 (18)	C9—C10	1.3855 (17)
C1—C2	1.3919 (17)	C9—H9	0.9500
C1—C6	1.4123 (17)	C10—C11	1.3870 (18)
C2—C3	1.3905 (18)	C10—H10	0.9500
C2—H2A	0.9500	C11—C12	1.3857 (18)
C3—C4	1.3958 (19)	C12—C13	1.3901 (17)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.3859 (17)	C13—H13	0.9500
C4—H4	0.9500

C1—O1—H1	106.7 (14)	C1—C6—C7	122.36 (11)
C7—N1—N2	117.40 (10)	N1—C7—C6	121.41 (11)
N1—N2—C8	121.06 (10)	N1—C7—H7	119.3
N1—N2—H2	117.2 (11)	C6—C7—H7	119.3
C8—N2—H2	121.0 (11)	N2—C8—C9	118.24 (11)
O1—C1—C2	118.08 (11)	N2—C8—C13	122.42 (11)
O1—C1—C6	121.69 (11)	C9—C8—C13	119.33 (11)
C2—C1—C6	120.22 (11)	C10—C9—C8	120.76 (11)
C1—C2—C3	120.17 (11)	C10—C9—H9	119.6
C1—C2—H2A	119.9	C8—C9—H9	119.6
C3—C2—H2A	119.9	C9—C10—C11	119.17 (11)
C2—C3—C4	120.51 (11)	C9—C10—H10	120.4
C2—C3—H3	119.7	C11—C10—H10	120.4
C4—C3—H3	119.7	C10—C11—C12	121.02 (11)
C5—C4—C3	119.15 (11)	C10—C11—Cl1	119.62 (9)
C5—C4—H4	120.4	C12—C11—Cl1	119.36 (10)
C3—C4—H4	120.4	C11—C12—C13	119.83 (12)
C4—C5—C6	121.68 (11)	C11—C12—H12	120.1
C4—C5—H5	119.2	C13—C12—H12	120.1
C6—C5—H5	119.2	C12—C13—C8	119.88 (11)
C5—C6—C1	118.27 (11)	C12—C13—H13	120.1
C5—C6—C7	119.37 (11)	C8—C13—H13	120.1

C7—N1—N2—C8	−171.80 (11)	C1—C6—C7—N1	0.68 (18)
O1—C1—C2—C3	179.94 (11)	N1—N2—C8—C9	168.57 (11)
C6—C1—C2—C3	−1.21 (19)	N1—N2—C8—C13	−12.10 (18)
C1—C2—C3—C4	1.21 (19)	N2—C8—C9—C10	178.83 (12)
C2—C3—C4—C5	−0.44 (18)	C13—C8—C9—C10	−0.52 (18)
C3—C4—C5—C6	−0.32 (18)	C8—C9—C10—C11	0.32 (19)
C4—C5—C6—C1	0.31 (18)	C9—C10—C11—C12	0.10 (19)
C4—C5—C6—C7	−179.31 (11)	C9—C10—C11—Cl1	179.78 (10)
O1—C1—C6—C5	179.26 (11)	C10—C11—C12—C13	−0.30 (19)
C2—C1—C6—C5	0.46 (18)	Cl1—C11—C12—C13	−179.99 (10)
O1—C1—C6—C7	−1.13 (18)	C11—C12—C13—C8	0.10 (18)
C2—C1—C6—C7	−179.93 (11)	N2—C8—C13—C12	−179.01 (11)
N2—N1—C7—C6	179.85 (10)	C9—C8—C13—C12	0.31 (18)
C5—C6—C7—N1	−179.72 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (2)	1.88 (2)	2.6382 (13)	149.8 (19)
N2—H2···Cg1ⁱ	0.859 (18)	2.73 (2)	3.3675 (12)	132.3 (17)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClN₂O
M_r	246.69
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	10.7590 (1), 7.3189 (1), 28.9222 (3)
V (Å³)	2277.45 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.25 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.925, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	20107, 2614, 2326
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.04
No. of reflections	2614
No. of parameters	162
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.19

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (2)	1.88 (2)	2.6382 (13)	149.8 (19)
N2—H2···Cg1ⁱ	0.859 (18)	2.73 (2)	3.3675 (12)	132.3 (17)

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

Acknowledgements

We thank the University of Malaya (grant No. RG020/09AFR) for supporting this study.

References

Auwers, K. (1909). Justus Liebigs Ann. Chem. 365, 314–342. CrossRef CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1452

doi:10.1107/S1600536811017958

Open

access