2,2′-Dichloro-N,N′-[1,3-phenyl­enebis(methyl­ene)]diacetamide

Cai, H.-X.; Wu, W.-N.

doi:10.1107/S1600536812008653

organic compounds

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Volume 68| Part 4| April 2012| Page o933

doi:10.1107/S1600536812008653

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2,2′-Dichloro-N,N′-[1,3-phenylenebis(methylene)]diacetamide

Hong-Xin Cai ^a and Wei-Na Wu ^a ^*

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People's Republic of China
^*Correspondence e-mail: wuwn08@hpu.edu.cn

(Received 24 February 2012; accepted 27 February 2012; online 3 March 2012)

The complete molecule of the title compound, C₁₂H₁₄Cl₂N₂O₂, is generated by a crystallographic twofold axis with two C atoms of the central benzene ring lying on the axis. In the crystal, N—H⋯O hydrogen bonds link the molecules into chains parallel to the c axis.

Related literature

For the synthesis of lanthanide complexes with amide-type ligands, see: Wu et al. (2008 ). For a related structure, see: Yuan et al. (2010 ).

Experimental

Crystal data

C₁₂H₁₄Cl₂N₂O₂
M_r = 289.15
Monoclinic, C 2/c
a = 20.62 (2) Å
b = 7.464 (8) Å
c = 9.485 (11) Å
β = 110.362 (11)°
V = 1369 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.27 × 0.23 × 0.22 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.881, T_max = 0.902
6996 measured reflections
1574 independent reflections
1288 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.157
S = 1.06
1574 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1ⁱ	0.86	2.03	2.864 (3)	163
Symmetry code: (i) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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 I, global. DOI: 10.1107/S1600536812008653/vm2160sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008653/vm2160Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008653/vm2160Isup3.cml

checkCIF report

Comment top

The luminescent properties of the lanthanide complexes with amide type ligands have been investigated in our previous work (Wu et al., 2008). As part of our ongoing studies of the amide type ligands, the title compound was synthesized and characterized by X-ray diffraction.

The complete molecule of the title compound (Fig. 1) is generated by a crystallographic twofold axis with atoms C5 and C7 of the central phenyl group lying on the axis. All the bond lengths are comparable with those observed in a similar compound (Yuan et al., 2010). In the crystal, intermolecular N—H···O hydrogen bonds link the molecules into chains parallel to the c axis (Table 1).

Related literature top

For the synthesis of lanthanide complexes with amide-type ligands, see: Wu et al. (2008). For a related structure, see: Yuan et al. (2010).

Experimental top

A chloroform solution containing chloroacetyl chloride (2.26 g, 0.02 mol) was added dropwise to a solution of (3-(aminomethyl)phenyl)methanamine (1.36 g, 0.01 mol) and pyridine (1.60 g, 0.02 mol) in chloroform (20 ml) under stirring on a ice-water bath. Then, the reaction mixture was stirred at room temperature for 3.5 h. A solid product was separated from the solution by suction filtration, purified by washing with water, 0.5 mol/L HCl, 0.5 mol/L NaOH and distilled water, respectively. Colourless prism crystals were obtained by slow evaporation of the acetone solution at room temperature.

Structure description top

For the synthesis of lanthanide complexes with amide-type ligands, see: Wu et al. (2008). For a related structure, see: Yuan et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 shown with 50% probability displacement ellipsoids. Unlabelled atoms are related with the labelled ones by symmetry operation (-x, y, -z - 1/2).

2,2'-Dichloro-N,N'-[1,3-phenylenebis(methylene)]diacetamide top

Crystal data top

C₁₂H₁₄Cl₂N₂O₂	F(000) = 600
M_r = 289.15	D_x = 1.403 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1673 reflections
a = 20.62 (2) Å	θ = 2.1–27.5°
b = 7.464 (8) Å	µ = 0.47 mm⁻¹
c = 9.485 (11) Å	T = 296 K
β = 110.362 (11)°	Prism, colorless
V = 1369 (3) Å³	0.27 × 0.23 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	1574 independent reflections
Radiation source: fine-focus sealed tube	1288 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
φ and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −26→26
T_min = 0.881, T_max = 0.902	k = −9→9
6996 measured reflections	l = −12→12

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0746P)² + 0.9706P] where P = (F_o² + 2F_c²)/3
1574 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₂H₁₄Cl₂N₂O₂	V = 1369 (3) Å³
M_r = 289.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.62 (2) Å	µ = 0.47 mm⁻¹
b = 7.464 (8) Å	T = 296 K
c = 9.485 (11) Å	0.27 × 0.23 × 0.22 mm
β = 110.362 (11)°

Data collection top

Bruker SMART APEX CCD diffractometer	1574 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1288 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.902	R_int = 0.080
6996 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.06	Δρ_max = 0.46 e Å⁻³
1574 reflections	Δρ_min = −0.31 e Å⁻³
83 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	0.28959 (11)	−0.0305 (3)	0.6316 (2)	0.0460 (5)
H1A	0.2913	0.0011	0.5338	0.055*
H1B	0.2936	−0.1597	0.6422	0.055*
C2	0.22101 (10)	0.0300 (3)	0.6421 (2)	0.0399 (5)
C3	0.10062 (11)	0.1072 (4)	0.4959 (3)	0.0635 (8)
H3A	0.0938	0.2349	0.4780	0.076*
H3B	0.0931	0.0795	0.5889	0.076*
C4	0.04867 (10)	0.0058 (3)	0.3676 (2)	0.0443 (5)
C5	0.0000	0.0960 (4)	0.2500	0.0429 (7)
H5	0.0000	0.2206	0.2500	0.052*
C6	0.04839 (12)	−0.1788 (4)	0.3656 (3)	0.0599 (7)
H6	0.0810	−0.2418	0.4427	0.072*
C7	0.0000	−0.2710 (5)	0.2500	0.0701 (11)
H7	0.0000	−0.3956	0.2500	0.084*
N1	0.17173 (9)	0.0598 (3)	0.51078 (19)	0.0526 (6)
H1C	0.1819	0.0510	0.4305	0.063*
O1	0.21270 (9)	0.0449 (3)	0.76351 (17)	0.0564 (5)
Cl1	0.35925 (3)	0.07271 (11)	0.77441 (8)	0.0728 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0388 (11)	0.0610 (13)	0.0346 (10)	−0.0002 (9)	0.0081 (8)	−0.0056 (9)
C2	0.0372 (10)	0.0537 (12)	0.0294 (9)	−0.0106 (8)	0.0123 (8)	−0.0037 (8)
C3	0.0341 (11)	0.113 (2)	0.0410 (11)	0.0022 (12)	0.0095 (9)	−0.0225 (13)
C4	0.0299 (9)	0.0698 (14)	0.0344 (10)	0.0022 (9)	0.0129 (8)	−0.0017 (9)
C5	0.0319 (14)	0.0550 (18)	0.0414 (14)	0.000	0.0120 (12)	0.000
C6	0.0376 (11)	0.0767 (18)	0.0620 (14)	0.0108 (11)	0.0133 (10)	0.0208 (12)
C7	0.0496 (19)	0.052 (2)	0.108 (3)	0.000	0.027 (2)	0.000
N1	0.0323 (9)	0.0990 (17)	0.0264 (8)	−0.0014 (9)	0.0101 (7)	−0.0088 (8)
O1	0.0523 (10)	0.0911 (14)	0.0281 (7)	−0.0061 (8)	0.0170 (7)	−0.0022 (7)
Cl1	0.0404 (4)	0.1002 (6)	0.0649 (5)	−0.0068 (3)	0.0021 (3)	−0.0226 (4)

Geometric parameters (Å, º) top

C1—C2	1.520 (3)	C4—C6	1.378 (4)
C1—Cl1	1.771 (2)	C4—C5	1.388 (3)
C1—H1A	0.9700	C5—C4ⁱ	1.388 (3)
C1—H1B	0.9700	C5—H5	0.9300
C2—O1	1.227 (3)	C6—C7	1.382 (3)
C2—N1	1.324 (3)	C6—H6	0.9300
C3—N1	1.467 (3)	C7—C6ⁱ	1.382 (3)
C3—C4	1.514 (3)	C7—H7	0.9300
C3—H3A	0.9700	N1—H1C	0.8600
C3—H3B	0.9700

C2—C1—Cl1	110.26 (16)	C6—C4—C5	118.4 (2)
C2—C1—H1A	109.6	C6—C4—C3	120.6 (2)
Cl1—C1—H1A	109.6	C5—C4—C3	121.0 (2)
C2—C1—H1B	109.6	C4ⁱ—C5—C4	122.0 (3)
Cl1—C1—H1B	109.6	C4ⁱ—C5—H5	119.0
H1A—C1—H1B	108.1	C4—C5—H5	119.0
O1—C2—N1	123.7 (2)	C4—C6—C7	120.5 (2)
O1—C2—C1	121.7 (2)	C4—C6—H6	119.8
N1—C2—C1	114.53 (19)	C7—C6—H6	119.8
N1—C3—C4	111.2 (2)	C6—C7—C6ⁱ	120.3 (4)
N1—C3—H3A	109.4	C6—C7—H7	119.9
C4—C3—H3A	109.4	C6ⁱ—C7—H7	119.9
N1—C3—H3B	109.4	C2—N1—C3	123.07 (19)
C4—C3—H3B	109.4	C2—N1—H1C	118.5
H3A—C3—H3B	108.0	C3—N1—H1C	118.5

Cl1—C1—C2—O1	−41.4 (3)	C5—C4—C6—C7	−0.9 (3)
Cl1—C1—C2—N1	140.17 (19)	C3—C4—C6—C7	178.68 (18)
N1—C3—C4—C6	58.1 (3)	C4—C6—C7—C6ⁱ	0.47 (15)
N1—C3—C4—C5	−122.3 (2)	O1—C2—N1—C3	−2.6 (4)
C6—C4—C5—C4ⁱ	0.46 (14)	C1—C2—N1—C3	175.8 (2)
C3—C4—C5—C4ⁱ	−179.1 (2)	C4—C3—N1—C2	−137.0 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱⁱ	0.86	2.03	2.864 (3)	163

Symmetry code: (ii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄Cl₂N₂O₂
M_r	289.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	20.62 (2), 7.464 (8), 9.485 (11)
β (°)	110.362 (11)
V (Å³)	1369 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.27 × 0.23 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.881, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	6996, 1574, 1288
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.157, 1.06
No. of reflections	1574
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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
N1—H1C···O1ⁱ	0.86	2.03	2.864 (3)	163.0

Symmetry code: (i) x, −y, z−1/2.

Acknowledgements

The authors are grateful for financial support from the Doctoral Foundation of Henan Polytechnic University (B2009–65 648359 and B2009–70 648364).

References

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