(Z)-N-(2-Chloro­benzyl­idene)aniline N-oxide

Fu, Y.; Liu, Y.; Yang, Y.; Chen, Y.

doi:10.1107/S1600536811015923

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1320

doi:10.1107/S1600536811015923

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(Z)-N-(2-Chlorobenzylidene)aniline N-oxide

Ying Fu,^a ^* Yanhua Liu,^a Yanshou Yang ^a and Yaojuan Chen ^a

^aKey Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, An'ning East Road No. 967, Gansu Province 730070, People's Republic of China
^*Correspondence e-mail: fu_yingmail@126.com

(Received 16 March 2011; accepted 27 April 2011; online 7 May 2011)

In the title compound, C₁₃H₁₀ClNO, the central C—N bond has considerable double-bond character and the N—O bond indicates a formal negative charge on the O atom. The molecule is stabilized by an intramolecular C—H⋯O hydrogen bond. The geometry about the C=N bond is Z [C—C—N—O torsion angle = −4.2 (3)°] and the phenyl and benzene rings are trans-oriented around the C=N bond. The phenyl and benzene rings make a dihedral angle of 56.99 (2)°.

Related literature

For the crystal structures of diphenyl nitrone derivatives, see: Vijayalakshmi et al. (1997 , 2000 ); Kang et al. (2000 ); Bedford et al. (1991 ); Mothi Mohamed et al. (2003 ); Brown & Trefonas (1973 ); Chandrasekar & Panchanatheswaran (2000 ).

Experimental

Crystal data

C₁₃H₁₀ClNO
M_r = 231.67
Monoclinic, P 2₁ /c
a = 9.7302 (3) Å
b = 9.7389 (3) Å
c = 11.7460 (3) Å
β = 104.093 (1)°
V = 1079.57 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.45 × 0.42 × 0.41 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.866, T_max = 0.877
6083 measured reflections
2232 independent reflections
1904 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.136
S = 1.05
2232 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1	0.93	2.26	2.857 (2)	121

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015923/bx2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015923/bx2346Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015923/bx2346Isup3.cml

checkCIF report

Comment top

In the crystal structure of the title compound, (I) the bond lenghts C=N and N—O are 1.304 (2) and 1.2933 (16) Å respectively which are similar to the values observed in other nitrones compounds (Vijayalakshmi, et al., 1997 and 2000). The central moiety is planar as seen in the C6—C7—N1—C8 torsion angle of 178.20 (14)° . The phenyl and benzene substituents are twisted out of this plane by 47.4 (2) ) and 14.3( 2)° respectively and are oriented trans conformation respect to the C=N bond. Two short intermolecular contact are observed, Cl···H3ⁱ 2.884 Å and C12···C6ⁱ 3.382 (2)Å [symmetry code: (i) x, 1.5-y, -1/2+z].

Related literature top

For the crystal structures of diphenyl nitrone derivatives, see: Vijayalakshmi et al. (1997, 2000); Kang et al. (2000); Bedford et al. (1991); Mothi Mohamed et al. (2003); Brown & Trefonas (1973); Chandrasekar & Panchanatheswaran (2000).

Experimental top

A solution of 2-chlorobenzaldehyde (2.80 g) was added dropwise with stirring to a solution of N-phenylhydroxylamine (2.1 g) in ethanol (20 ml). The mixture was heated for about 1 h at 333 K. The crystals were crystallized from ethanol [m.p. 426 K; yield 1.90 g (82%)].

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids.

(Z)-N-(2-Chlorobenzylidene)aniline N-oxide top

Crystal data top

C₁₃H₁₀ClNO	F(000) = 480
M_r = 231.67	D_x = 1.425 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 362 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.7302 (3) Å	Cell parameters from 2703 reflections
b = 9.7389 (3) Å	θ = 2.8–29.3°
c = 11.7460 (3) Å	µ = 0.33 mm⁻¹
β = 104.093 (1)°	T = 296 K
V = 1079.57 (5) Å³	Block, yellow
Z = 4	0.45 × 0.42 × 0.41 mm

Data collection top

Bruker APEXII CCD diffractometer	2232 independent reflections
Radiation source: fine-focus sealed tube	1904 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −12→12
T_min = 0.866, T_max = 0.877	k = −11→12
6083 measured reflections	l = −14→14

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2232 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₁₀ClNO	V = 1079.57 (5) Å³
M_r = 231.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7302 (3) Å	µ = 0.33 mm⁻¹
b = 9.7389 (3) Å	T = 296 K
c = 11.7460 (3) Å	0.45 × 0.42 × 0.41 mm
β = 104.093 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2232 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1904 reflections with I > 2σ(I)
T_min = 0.866, T_max = 0.877	R_int = 0.027
6083 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2232 reflections	Δρ_min = −0.28 e Å⁻³
145 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
C1	0.59092 (15)	0.85392 (16)	1.09921 (12)	0.0398 (4)
C2	0.55547 (18)	0.86628 (18)	1.20546 (14)	0.0493 (4)
H2	0.4895	0.8070	1.2245	0.059*
C3	0.6185 (2)	0.96710 (19)	1.28344 (15)	0.0544 (4)
H3	0.5941	0.9766	1.3548	0.065*
C4	0.7169 (2)	1.05308 (19)	1.25583 (14)	0.0558 (5)
H4	0.7610	1.1192	1.3095	0.067*
C5	0.75133 (19)	1.04225 (18)	1.14841 (13)	0.0482 (4)
H5	0.8172	1.1024	1.1304	0.058*
C6	0.68853 (15)	0.94220 (16)	1.06663 (12)	0.0387 (3)
C7	0.72415 (16)	0.92349 (15)	0.95480 (13)	0.0409 (4)
H7	0.6940	0.8423	0.9147	0.049*
C8	0.82470 (16)	0.97275 (16)	0.79355 (13)	0.0401 (4)
C9	0.80082 (18)	1.07137 (17)	0.70579 (14)	0.0490 (4)
H9	0.7639	1.1567	0.7181	0.059*
C10	0.8323 (2)	1.0418 (2)	0.60028 (15)	0.0566 (5)
H10	0.8157	1.1068	0.5404	0.068*
C11	0.88845 (18)	0.9152 (2)	0.58376 (15)	0.0546 (5)
H11	0.9096	0.8953	0.5125	0.066*
C12	0.91332 (18)	0.8187 (2)	0.67115 (16)	0.0523 (4)
H12	0.9519	0.7342	0.6591	0.063*
C13	0.88125 (16)	0.84651 (17)	0.77743 (14)	0.0465 (4)
H13	0.8976	0.7811	0.8369	0.056*
Cl1	0.51025 (5)	0.72300 (5)	1.00632 (4)	0.0567 (2)
N1	0.79421 (14)	1.00909 (12)	0.90471 (11)	0.0434 (3)
O1	0.83697 (18)	1.12972 (13)	0.94397 (11)	0.0729 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0408 (7)	0.0398 (8)	0.0400 (8)	0.0037 (6)	0.0119 (6)	0.0026 (6)
C2	0.0545 (9)	0.0499 (9)	0.0490 (9)	0.0006 (7)	0.0230 (7)	0.0042 (7)
C3	0.0740 (11)	0.0569 (10)	0.0386 (8)	0.0025 (9)	0.0254 (8)	0.0026 (8)
C4	0.0775 (12)	0.0533 (10)	0.0367 (8)	−0.0070 (9)	0.0140 (8)	−0.0028 (8)
C5	0.0608 (10)	0.0469 (9)	0.0389 (8)	−0.0080 (8)	0.0161 (7)	0.0020 (7)
C6	0.0421 (7)	0.0386 (8)	0.0361 (7)	0.0033 (6)	0.0111 (6)	0.0049 (6)
C7	0.0458 (8)	0.0403 (8)	0.0383 (7)	−0.0029 (6)	0.0132 (6)	0.0007 (6)
C8	0.0415 (8)	0.0437 (8)	0.0381 (8)	−0.0054 (6)	0.0152 (6)	−0.0007 (6)
C9	0.0598 (10)	0.0455 (9)	0.0457 (9)	0.0042 (7)	0.0207 (8)	0.0052 (7)
C10	0.0655 (11)	0.0657 (11)	0.0422 (9)	−0.0025 (9)	0.0196 (8)	0.0061 (8)
C11	0.0540 (10)	0.0695 (12)	0.0454 (9)	−0.0114 (8)	0.0219 (7)	−0.0129 (8)
C12	0.0464 (9)	0.0498 (9)	0.0644 (11)	−0.0030 (7)	0.0208 (8)	−0.0153 (8)
C13	0.0477 (8)	0.0439 (8)	0.0506 (9)	−0.0010 (7)	0.0175 (7)	0.0016 (7)
Cl1	0.0618 (3)	0.0572 (3)	0.0559 (3)	−0.01765 (19)	0.0235 (2)	−0.01032 (18)
N1	0.0543 (8)	0.0394 (7)	0.0406 (7)	−0.0058 (5)	0.0192 (6)	−0.0017 (5)
O1	0.1234 (12)	0.0490 (8)	0.0603 (8)	−0.0311 (8)	0.0496 (8)	−0.0134 (6)

Geometric parameters (Å, º) top

C1—C2	1.379 (2)	C8—C13	1.379 (2)
C1—C6	1.402 (2)	C8—C9	1.387 (2)
C1—Cl1	1.7364 (16)	C8—N1	1.451 (2)
C2—C3	1.380 (3)	C9—C10	1.377 (2)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.369 (3)	C10—C11	1.381 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.386 (2)	C11—C12	1.369 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.400 (2)	C12—C13	1.385 (2)
C5—H5	0.9300	C12—H12	0.9300
C6—C7	1.449 (2)	C13—H13	0.9300
C7—N1	1.304 (2)	N1—O1	1.2933 (16)
C7—H7	0.9300

C2—C1—C6	121.95 (14)	C13—C8—C9	121.05 (15)
C2—C1—Cl1	117.28 (12)	C13—C8—N1	121.12 (13)
C6—C1—Cl1	120.77 (11)	C9—C8—N1	117.77 (14)
C1—C2—C3	119.60 (16)	C10—C9—C8	119.38 (17)
C1—C2—H2	120.2	C10—C9—H9	120.3
C3—C2—H2	120.2	C8—C9—H9	120.3
C4—C3—C2	120.09 (16)	C9—C10—C11	119.67 (17)
C4—C3—H3	120.0	C9—C10—H10	120.2
C2—C3—H3	120.0	C11—C10—H10	120.2
C3—C4—C5	120.47 (16)	C12—C11—C10	120.74 (16)
C3—C4—H4	119.8	C12—C11—H11	119.6
C5—C4—H4	119.8	C10—C11—H11	119.6
C4—C5—C6	121.05 (16)	C11—C12—C13	120.26 (17)
C4—C5—H5	119.5	C11—C12—H12	119.9
C6—C5—H5	119.5	C13—C12—H12	119.9
C5—C6—C1	116.82 (14)	C8—C13—C12	118.89 (16)
C5—C6—C7	123.27 (14)	C8—C13—H13	120.6
C1—C6—C7	119.85 (13)	C12—C13—H13	120.6
N1—C7—C6	126.52 (14)	O1—N1—C7	125.30 (14)
N1—C7—H7	116.7	O1—N1—C8	115.07 (12)
C6—C7—H7	116.7	C7—N1—C8	119.58 (13)

C6—C1—C2—C3	−0.8 (2)	N1—C8—C9—C10	178.21 (15)
Cl1—C1—C2—C3	178.84 (13)	C8—C9—C10—C11	−0.7 (3)
C1—C2—C3—C4	−0.8 (3)	C9—C10—C11—C12	0.0 (3)
C2—C3—C4—C5	1.7 (3)	C10—C11—C12—C13	0.5 (3)
C3—C4—C5—C6	−1.1 (3)	C9—C8—C13—C12	−0.5 (2)
C4—C5—C6—C1	−0.5 (2)	N1—C8—C13—C12	−177.63 (14)
C4—C5—C6—C7	−177.88 (16)	C11—C12—C13—C8	−0.3 (2)
C2—C1—C6—C5	1.4 (2)	C6—C7—N1—O1	−4.2 (3)
Cl1—C1—C6—C5	−178.22 (12)	C6—C7—N1—C8	178.20 (14)
C2—C1—C6—C7	178.92 (14)	C13—C8—N1—O1	133.68 (16)
Cl1—C1—C6—C7	−0.7 (2)	C9—C8—N1—O1	−43.6 (2)
C5—C6—C7—N1	−14.5 (2)	C13—C8—N1—C7	−48.5 (2)
C1—C6—C7—N1	168.21 (15)	C9—C8—N1—C7	134.23 (16)
C13—C8—C9—C10	0.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.93	2.26	2.857 (2)	121
C7—H7···Cl1	0.93	2.58	3.0206 (16)	110

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀ClNO
M_r	231.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.7302 (3), 9.7389 (3), 11.7460 (3)
β (°)	104.093 (1)
V (Å³)	1079.57 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.45 × 0.42 × 0.41

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.866, 0.877
No. of measured, independent and observed [I > 2σ(I)] reflections	6083, 2232, 1904
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.136, 1.05
No. of reflections	2232
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.93	2.26	2.857 (2)	121
C7—H7···Cl1	0.93	2.58	3.0206 (16)	110

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (No. 20962017) and the Natural Science Foundation of Gansu Province, China (No. 2007GS03630)

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