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

Abstract

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,

• a = 20.62 (2) Å

• b = 7.464 (8) Å

• c = 9.485 (11) Å

• β = 110.362 (11)°

• V = 1369 (3) ų

• 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[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812008653/vm2160Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms were placed at calculated positions and refined in riding mode, with the carrier atom-H distances = 0.93 Å for aryl, 0.97 Å for methylene and 0.86 Å for the secondary amine H atoms. The U_iso values were constrained to be 1.2U_eq of the carrier atom for the H atoms.

Figures

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).

Crystal data

C12H14Cl2N2O2	F(000) = 600
Mr = 289.15	Dx = 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

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

Refinement

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(Fo2) + (0.0746P)2 + 0.9706P] where P = (Fo2 + 2Fc2)/3
1574 reflections	(Δ/σ)max < 0.001
83 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.