(E)-(2-Chloro­benzyl­idene)amino 2-amino-4-chloro­benzoate

Yin, W.; Wang, Z.; Liang, Y.; Yang, Z.-W.

doi:10.1107/S1600536812003844

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o770

doi:10.1107/S1600536812003844

Open

access

(E)-(2-Chlorobenzylidene)amino 2-amino-4-chlorobenzoate

Weiyan Yin,^a ^* Zhi Wang,^a Ying Liang ^a and Zi-Wen Yang ^a

^aHubei Biopesticide Engineering Research Center, Hubei Academy of Agricultural Science, Wuhan 430064, People's Republic of China
^*Correspondence e-mail: yinweiyan_2004@163.com

(Received 29 December 2011; accepted 29 January 2012; online 17 February 2012)

In the title compound, C₁₄H₁₀Cl₂N₂O₂, the configuration about the C=N double bond is E and the dihedral angle between the benzene rings is 1.75 (5)°. An intramolecular N—H⋯O interaction generates an S(6) ring. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, resulting in [101] chains.

Related literature

For background to 2-amino-4-chlorobenzoic acid derivatives, see: Jahnke et al. (2010 ); Lee et al. (2005 ). For a related structure, see: Seong et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₀Cl₂N₂O₂
M_r = 309.14
Monoclinic, P 2₁ /n
a = 7.4034 (5) Å
b = 23.8190 (15) Å
c = 7.6362 (5) Å
β = 96.382 (1)°
V = 1338.23 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 K
0.16 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.926, T_max = 0.953
12076 measured reflections
3879 independent reflections
3637 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.084
S = 1.05
3879 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O2	0.88	2.02	2.6653 (12)	130
N2—H2A⋯O2ⁱ	0.88	2.19	2.9332 (12)	142
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003844/hb6586sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003844/hb6586Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003844/hb6586Isup3.cml

checkCIF report

Comment top

2-Amino-4-chlorobenzoic acid derivatives show diverse biological properties such as inhibitor of the prostaglandin H2 synthase peroxidase activity (Lee et al., 2005) and allosteric inhibitors of Bcr-Abl (Jahnke et al., 2010). As a part of our studies of 2-aminobenzoic acid-containing compounds with potential biological activities, we report here the crystal structure of the title compound, (I) (Fig. 1).

The conformation of the N—H and the C=O bonds in the 2-aminobenzoic acid segment is similar to that observed in other 2-aminobenzoic acid compound (Seong et al., 2008). The dihedral angles between the two phenyl rings is 1.75 (5)°. The molecular structure is linked by N—H···O hydrogen-bonds (Table 1).

Related literature top

For background to 2-amino-4-chlorobenzoic acid derivatives, see: Jahnke et al. (2010); Lee et al. (2005). For a related structure, see: Seong et al. (2008).

Experimental top

Dicyclohexylcarbodiimide (1.1 g, 5.0 mmol) and 4-dimethylamiopryidine(0.25 g, 1.0 mmol) was added to a mixture of 2-chlorobenzaldehyde oxime (0.78 g, 5.0 mmol) and 2-amino-4-chlorobenzoic acid (0.86 g, 5.0 mmol) in dichloromethane (30 ml). The reaction mixture was stirred for 14 h at 353 k. The product was collected by filtration give a gray solid and recrystallization from its ether solution yielded colourless prisms of (I) after a few days.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Crystal Packing diagram of (I). Hydrogen bonds are shown as dashed lines.

(E)-(2-Chlorobenzylidene)amino 2-amino-4-chlorobenzoate top

Crystal data top

C₁₄H₁₀Cl₂N₂O₂	F(000) = 632
M_r = 309.14	D_x = 1.534 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4034 (5) Å	Cell parameters from 9848 reflections
b = 23.8190 (15) Å	θ = 2.8–32.0°
c = 7.6362 (5) Å	µ = 0.49 mm⁻¹
β = 96.382 (1)°	T = 100 K
V = 1338.23 (15) Å³	Block, colorless
Z = 4	0.16 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3879 independent reflections
Radiation source: fine-focus sealed tube	3637 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.926, T_max = 0.953	k = −33→32
12076 measured reflections	l = −10→10

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0495P)² + 0.5103P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3879 reflections	Δρ_max = 0.53 e Å⁻³
182 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0048 (10)

Crystal data top

C₁₄H₁₀Cl₂N₂O₂	V = 1338.23 (15) Å³
M_r = 309.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4034 (5) Å	µ = 0.49 mm⁻¹
b = 23.8190 (15) Å	T = 100 K
c = 7.6362 (5) Å	0.16 × 0.15 × 0.10 mm
β = 96.382 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3879 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3637 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.953	R_int = 0.015
12076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.05	Δρ_max = 0.53 e Å⁻³
3879 reflections	Δρ_min = −0.53 e Å⁻³
182 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	0.45478 (14)	0.08217 (4)	0.17648 (13)	0.01523 (18)
C2	0.36816 (14)	0.09752 (5)	0.01219 (13)	0.01805 (19)
H2	0.3133	0.0698	−0.0659	0.022*
C3	0.36279 (15)	0.15379 (5)	−0.03640 (14)	0.0197 (2)
H3	0.3043	0.1646	−0.1483	0.024*
C4	0.44295 (15)	0.19433 (5)	0.07849 (14)	0.0190 (2)
H4	0.4383	0.2328	0.0453	0.023*
C5	0.52956 (14)	0.17850 (4)	0.24135 (13)	0.01681 (19)
H5	0.5854	0.2063	0.3184	0.020*
C6	0.53611 (13)	0.12204 (4)	0.29440 (13)	0.01445 (18)
C7	0.62742 (13)	0.10574 (4)	0.46828 (13)	0.01528 (18)
H7	0.6660	0.0682	0.4918	0.018*
C9	0.80555 (13)	0.16068 (4)	0.86039 (13)	0.01431 (18)
C10	0.89159 (13)	0.13801 (4)	1.02756 (13)	0.01340 (17)
C11	0.97488 (13)	0.17569 (4)	1.15683 (13)	0.01466 (18)
C12	1.05960 (14)	0.15271 (4)	1.31596 (13)	0.01651 (19)
H12	1.1176	0.1767	1.4044	0.020*
C13	1.05789 (14)	0.09568 (4)	1.34250 (13)	0.01679 (19)
C14	0.97615 (14)	0.05787 (4)	1.21752 (14)	0.01768 (19)
H14	0.9772	0.0186	1.2394	0.021*
C15	0.89387 (13)	0.07991 (4)	1.06104 (13)	0.01523 (18)
H15	0.8374	0.0552	0.9739	0.018*
Cl1	0.45712 (4)	0.011502 (10)	0.23325 (3)	0.01985 (8)
Cl2	1.16302 (4)	0.069412 (12)	1.54105 (3)	0.02424 (8)
N1	0.65290 (13)	0.14358 (4)	0.58580 (12)	0.01819 (18)
N2	0.97461 (13)	0.23234 (4)	1.13648 (13)	0.02025 (19)
H2A	1.0264	0.2539	1.2213	0.024*
H2B	0.9226	0.2475	1.0385	0.024*
O1	0.74622 (10)	0.11954 (3)	0.74289 (10)	0.01663 (15)
O2	0.78875 (12)	0.21027 (3)	0.82487 (11)	0.02169 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0162 (4)	0.0151 (4)	0.0144 (4)	0.0010 (3)	0.0017 (3)	−0.0007 (3)
C2	0.0188 (4)	0.0214 (5)	0.0136 (4)	0.0015 (4)	−0.0002 (3)	−0.0026 (3)
C3	0.0209 (5)	0.0236 (5)	0.0145 (4)	0.0046 (4)	0.0011 (4)	0.0016 (4)
C4	0.0220 (5)	0.0179 (4)	0.0173 (4)	0.0025 (4)	0.0034 (4)	0.0030 (4)
C5	0.0192 (4)	0.0158 (4)	0.0156 (4)	−0.0005 (3)	0.0027 (3)	−0.0001 (3)
C6	0.0147 (4)	0.0159 (4)	0.0127 (4)	0.0010 (3)	0.0018 (3)	0.0001 (3)
C7	0.0158 (4)	0.0157 (4)	0.0140 (4)	−0.0002 (3)	0.0002 (3)	0.0006 (3)
C9	0.0131 (4)	0.0141 (4)	0.0151 (4)	−0.0011 (3)	−0.0016 (3)	0.0003 (3)
C10	0.0129 (4)	0.0133 (4)	0.0134 (4)	−0.0004 (3)	−0.0014 (3)	0.0004 (3)
C11	0.0134 (4)	0.0142 (4)	0.0160 (4)	−0.0009 (3)	−0.0001 (3)	−0.0010 (3)
C12	0.0155 (4)	0.0195 (5)	0.0139 (4)	−0.0010 (3)	−0.0008 (3)	−0.0010 (3)
C13	0.0150 (4)	0.0217 (5)	0.0133 (4)	0.0003 (3)	−0.0002 (3)	0.0041 (3)
C14	0.0181 (4)	0.0157 (4)	0.0187 (5)	−0.0008 (3)	−0.0003 (4)	0.0040 (3)
C15	0.0152 (4)	0.0134 (4)	0.0166 (4)	−0.0012 (3)	−0.0005 (3)	0.0009 (3)
Cl1	0.02618 (14)	0.01429 (12)	0.01833 (13)	−0.00055 (8)	−0.00089 (9)	−0.00137 (8)
Cl2	0.02529 (14)	0.03026 (15)	0.01581 (13)	−0.00042 (10)	−0.00378 (10)	0.00817 (9)
N1	0.0215 (4)	0.0180 (4)	0.0137 (4)	0.0028 (3)	−0.0036 (3)	0.0012 (3)
N2	0.0244 (4)	0.0134 (4)	0.0210 (4)	−0.0021 (3)	−0.0062 (3)	−0.0016 (3)
O1	0.0210 (4)	0.0146 (3)	0.0130 (3)	0.0009 (3)	−0.0041 (3)	−0.0002 (2)
O2	0.0264 (4)	0.0138 (3)	0.0223 (4)	−0.0026 (3)	−0.0090 (3)	0.0035 (3)

Geometric parameters (Å, º) top

C1—C2	1.3928 (14)	C9—C10	1.4649 (13)
C1—C6	1.3980 (14)	C10—C15	1.4071 (13)
C1—Cl1	1.7378 (10)	C10—C11	1.4230 (13)
C2—C3	1.3902 (15)	C11—N2	1.3581 (13)
C2—H2	0.9500	C11—C12	1.4143 (14)
C3—C4	1.3923 (15)	C12—C13	1.3736 (14)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.3866 (14)	C13—C14	1.3999 (15)
C4—H4	0.9500	C13—Cl2	1.7417 (10)
C5—C6	1.4039 (14)	C14—C15	1.3829 (14)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.4735 (14)	C15—H15	0.9500
C7—N1	1.2712 (13)	N1—O1	1.4352 (11)
C7—H7	0.9500	N2—H2A	0.8800
C9—O2	1.2151 (12)	N2—H2B	0.8800
C9—O1	1.3677 (12)

C2—C1—C6	121.62 (9)	C15—C10—C11	119.92 (9)
C2—C1—Cl1	118.01 (8)	C15—C10—C9	121.07 (9)
C6—C1—Cl1	120.37 (8)	C11—C10—C9	119.01 (9)
C3—C2—C1	119.34 (10)	N2—C11—C12	118.53 (9)
C3—C2—H2	120.3	N2—C11—C10	123.52 (9)
C1—C2—H2	120.3	C12—C11—C10	117.94 (9)
C2—C3—C4	120.20 (10)	C13—C12—C11	119.94 (9)
C2—C3—H3	119.9	C13—C12—H12	120.0
C4—C3—H3	119.9	C11—C12—H12	120.0
C5—C4—C3	119.92 (10)	C12—C13—C14	123.09 (9)
C5—C4—H4	120.0	C12—C13—Cl2	118.24 (8)
C3—C4—H4	120.0	C14—C13—Cl2	118.67 (8)
C4—C5—C6	121.13 (10)	C15—C14—C13	117.41 (9)
C4—C5—H5	119.4	C15—C14—H14	121.3
C6—C5—H5	119.4	C13—C14—H14	121.3
C1—C6—C5	117.79 (9)	C14—C15—C10	121.70 (9)
C1—C6—C7	121.54 (9)	C14—C15—H15	119.1
C5—C6—C7	120.67 (9)	C10—C15—H15	119.1
N1—C7—C6	117.81 (9)	C7—N1—O1	109.09 (8)
N1—C7—H7	121.1	C11—N2—H2A	120.0
C6—C7—H7	121.1	C11—N2—H2B	120.0
O2—C9—O1	122.17 (9)	H2A—N2—H2B	120.0
O2—C9—C10	125.21 (9)	C9—O1—N1	110.62 (7)
O1—C9—C10	112.61 (8)

C6—C1—C2—C3	0.25 (16)	C15—C10—C11—N2	−178.31 (10)
Cl1—C1—C2—C3	179.50 (8)	C9—C10—C11—N2	2.12 (15)
C1—C2—C3—C4	−0.16 (16)	C15—C10—C11—C12	0.59 (14)
C2—C3—C4—C5	0.48 (16)	C9—C10—C11—C12	−178.99 (9)
C3—C4—C5—C6	−0.89 (16)	N2—C11—C12—C13	178.24 (10)
C2—C1—C6—C5	−0.63 (15)	C10—C11—C12—C13	−0.71 (15)
Cl1—C1—C6—C5	−179.86 (8)	C11—C12—C13—C14	0.47 (16)
C2—C1—C6—C7	179.90 (9)	C11—C12—C13—Cl2	−179.67 (8)
Cl1—C1—C6—C7	0.66 (14)	C12—C13—C14—C15	−0.08 (16)
C4—C5—C6—C1	0.95 (15)	Cl2—C13—C14—C15	−179.94 (8)
C4—C5—C6—C7	−179.57 (9)	C13—C14—C15—C10	−0.04 (15)
C1—C6—C7—N1	−160.77 (10)	C11—C10—C15—C14	−0.22 (15)
C5—C6—C7—N1	19.77 (14)	C9—C10—C15—C14	179.35 (9)
O2—C9—C10—C15	175.68 (10)	C6—C7—N1—O1	−178.86 (8)
O1—C9—C10—C15	−5.26 (14)	O2—C9—O1—N1	−4.58 (14)
O2—C9—C10—C11	−4.74 (16)	C10—C9—O1—N1	176.34 (8)
O1—C9—C10—C11	174.31 (9)	C7—N1—O1—C9	168.81 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2	0.88	2.02	2.6653 (12)	130
N2—H2A···O2ⁱ	0.88	2.19	2.9332 (12)	142

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀Cl₂N₂O₂
M_r	309.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.4034 (5), 23.8190 (15), 7.6362 (5)
β (°)	96.382 (1)
V (Å³)	1338.23 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.16 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.926, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	12076, 3879, 3637
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.084, 1.05
No. of reflections	3879
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.53

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2	0.88	2.02	2.6653 (12)	130
N2—H2A···O2ⁱ	0.88	2.19	2.9332 (12)	142

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

Acknowledgements

The authors gratefully acknowledge financial support of this work by the Foundation of Hubei Agricultural Scientific and Technological Innovation.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jahnke, W., Grotzfeld, R. M., Pelle, X., Strauss, A., Fendrich, G., Cowan-Jacob, S. W., Cotesta, S., Fabbro, D., Furet, P., Mestan, D. & Marzinzik, A. L. (2010). J. Am. Chem. Soc. 132, 7043–7048. Web of Science CrossRef CAS PubMed Google Scholar
Lee, J., Chubb, A. J., Moman, E., McLoughlin, B. M., Sharkey, C. T., Kelly, J. G., Nolan, K. B., Devocelle, M. & Fitzgerald, D. J. (2005). Org. Biomol. Chem. 3, 3678–3685. Web of Science CrossRef PubMed CAS Google Scholar
Seong, C. M., Park, W. K., Park, C. M., Kong, J. Y. & Park, N. S. (2008). Bioorg. Med. Chem. Lett. 18, 738–743. 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