N,N′-(1,4-Phenyl­ene)bis­(4-chloro­butanamide)

Abstract

The title mol­ecule, C₁₄H₁₈Cl₂N₂O₂, lies on a crystallographic inversion center and the each 4-chloro­butanamide group adopts an anti-staggered conformation. In the crystal, adjacent mol­ecules are linked through N—H⋯O contacts, forming infinite ribbons extending parallel to the a axis.

Related literature

For details and syntheses of chloro­amides as precursors for new aza­macrocycles see: Benaglia et al. (2005 ▶); Harte & Gunnlaugsson (2006 ▶); Humphrey & Chamberlin (1997 ▶); Mangalagiu et al. (2007 ▶); Zbancioc et al. (2012 ▶).

Experimental

Crystal data

• C₁₄H₁₈Cl₂N₂O₂

• M _r = 317.20

• Triclinic,

• a = 5.105 (5) Å

• b = 6.876 (5) Å

• c = 10.549 (5) Å

• α = 97.735 (5)°

• β = 93.214 (5)°

• γ = 90.512 (5)°

• V = 366.3 (5) ų

• Z = 1

• Mo Kα radiation

• μ = 0.45 mm⁻¹

• T = 200 K

• 0.25 × 0.2 × 0.2 mm

Data collection

• Agilent Xcalibur Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.914, T _max = 1.000

• 2575 measured reflections

• 1446 independent reflections

• 1189 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.092

• S = 1.03

• 1446 reflections

• 91 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812001341/nk2130Isup3.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—H1⋯O1i	0.88	2.10	2.941 (3)	161

Symmetry code: (i) .

supplementary crystallographic information

Comment

With the aim of synthesizing new chloroamides as precursors for new azamacrocycles (Zbancioc et al., 2012), we report the synthesis and crystal structure of the title compound C₁₄H₁₈Cl₂N₂O₂, which represents a diamide with aliphatic arms, consisting of two moieties of butyryl chloride and a phenylenediamine unit. Amides are important building blocks in preparative macrocycle chemistry (Harte & Gunnlaugsson, 2006), due to their spectroscopic proprieties as well as to their arms ability to coordinate to metal centers. The X-ray structure of the title compound with the atom numbering scheme is shown in Fig. 1. The molecule is assembled from two centro-symmetrically related units through the C_i at the center of the aromatic ring. The amide group is rotated by 32.4 (2)° in respect with the phenyl ring. The butyryl chloride fragment adopts an anti-staggered conformation. The main crystal structure motif arises from the parallel packing of the ribbon (Fig. 2) along the crystallographic a axis. The infinite ribbons are stabilized via intermolecular N1—H1···O1ⁱⁱ H-bond with N1—H1 = 0.88 Å, N1···O1ⁱⁱ = 2.941 (3) Å, [symmetry code ii: x–1, y, z], H1···O1ⁱⁱ = 2.10 Å and N1HO1 angle of 161°.

Experimental

p-Phenylenediamine (5 mmol, 0.54 g) was dissolved in sodium hydroxide solution (0.4 N, 50 ml) and 4-chlorobutyryl chloride (30 mmol, 3.4 ml) was added dropwise under stirring at 0° C for 1 h. Afterwards the mixture was stirred at room temperature overnight resulting in a white precipitate, which was separated by filtration, washed several times with water and dried in vacuum; yield 60%. The purity of N,N'-(1,4-phenylene)bis(4-chlorobutanamide) was confirmed by ¹H and ¹³C NMR spectra.

¹H NMR (DMSO-d₆) δ (p.p.m.): 9.876 (s, 2NH), 7.492 (s, 4H, Ar), 3.675–3.708 (t, J = 6.8 Hz, 4H, CH₂, adjacent to chlor), 2.433–2.469 (t, J = 7.2 Hz, 4H, CH₂, adjacent to amido), 1.988–2.057 (c, J = 6.8 Hz J = 7.2 Hz, 4H, CH₂).

¹³C NMR (DMSO-d₆) δ (p.p.m.): 169.72 (2 C, C═O), 134.46 (2 C, Ar), 119.37 (4 C, Ar), 44.97 (2 C, CH₂, adjacent to chlor), 33.19 (2 C, CH₂, adjacent to amido), 27.90 (2 C, CH₂).

Refinement

The H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.99 Å and with U_iso(H) = 1.2 times U_eq(C).

Figures

Fig. 1.

The molecular structure of C14H18Cl2N2O2. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as small spheres of arbitrary radius. Symmetry code: (i) –x, –y+1, –z+1.

Fig. 2.

Part of the crystal structure of C14H18Cl2N2O2. Molecular chains generated by N—H···O hydrogen bonds are shown by dashed lines. H atoms not involved in intermolecular bonding have been omitted.

Crystal data

C14H18Cl2N2O2	Z = 1
Mr = 317.20	F(000) = 166
Triclinic, P1	Dx = 1.438 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.105 (5) Å	Cell parameters from 1244 reflections
b = 6.876 (5) Å	θ = 3.0–29.4°
c = 10.549 (5) Å	µ = 0.45 mm−1
α = 97.735 (5)°	T = 200 K
β = 93.214 (5)°	Prism, clear light yellow
γ = 90.512 (5)°	0.25 × 0.2 × 0.2 mm
V = 366.3 (5) Å3

Data collection

Agilent Xcalibur Eos diffractometer	1446 independent reflections
Radiation source: fine-focus sealed tube	1189 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 16.1593 pixels mm-1	θmax = 26.0°, θmin = 3.0°
ω scans	h = −5→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→7
Tmin = 0.914, Tmax = 1.000	l = −12→8
2575 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0387P)2 + 0.0691P] where P = (Fo2 + 2Fc2)/3
1446 reflections	(Δ/σ)max = 0.001
91 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.26 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
Cl1	0.29972 (11)	−0.27268 (9)	1.02884 (5)	0.0434 (2)
O1	0.4276 (2)	0.1286 (2)	0.67205 (14)	0.0337 (4)
C5	0.0022 (3)	0.3420 (3)	0.57107 (17)	0.0189 (4)
C6	−0.1885 (3)	0.4863 (3)	0.58668 (18)	0.0201 (4)
H6	−0.3186	0.4768	0.6466	0.024*
N1	−0.0077 (3)	0.1862 (2)	0.64528 (14)	0.0207 (4)
H1	−0.1645	0.1441	0.6607	0.025*
C2	0.3081 (3)	−0.2263 (3)	0.77558 (18)	0.0241 (4)
H2A	0.2956	−0.2923	0.6860	0.029*
H2B	0.4926	−0.1826	0.7966	0.029*
C1	0.2360 (4)	−0.3719 (3)	0.86319 (19)	0.0309 (5)
H1A	0.3385	−0.4927	0.8437	0.037*
H1B	0.0476	−0.4077	0.8477	0.037*
C4	0.2010 (3)	0.0948 (3)	0.69526 (18)	0.0206 (4)
C3	0.1331 (3)	−0.0471 (3)	0.78585 (18)	0.0229 (4)
H3A	−0.0520	−0.0909	0.7674	0.027*
H3B	0.1498	0.0214	0.8748	0.027*
C7	0.1922 (3)	0.3575 (3)	0.48302 (17)	0.0199 (4)
H7	0.3238	0.2610	0.4710	0.024*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0626 (4)	0.0419 (3)	0.0274 (3)	0.0172 (3)	0.0011 (3)	0.0104 (2)
O1	0.0155 (7)	0.0434 (9)	0.0481 (9)	0.0006 (6)	0.0023 (6)	0.0278 (7)
C5	0.0161 (8)	0.0198 (9)	0.0210 (10)	−0.0022 (7)	−0.0029 (7)	0.0060 (8)
C6	0.0154 (8)	0.0251 (10)	0.0203 (9)	−0.0005 (7)	0.0031 (7)	0.0045 (8)
N1	0.0148 (7)	0.0222 (8)	0.0269 (9)	−0.0006 (6)	0.0014 (6)	0.0102 (7)
C2	0.0237 (9)	0.0244 (10)	0.0254 (10)	0.0034 (8)	0.0017 (8)	0.0073 (8)
C1	0.0379 (11)	0.0248 (11)	0.0307 (12)	0.0049 (8)	−0.0020 (9)	0.0075 (9)
C4	0.0173 (9)	0.0206 (10)	0.0243 (10)	0.0012 (7)	−0.0004 (7)	0.0046 (8)
C3	0.0184 (8)	0.0252 (10)	0.0272 (10)	0.0042 (7)	0.0042 (8)	0.0104 (8)
C7	0.0158 (8)	0.0212 (9)	0.0230 (10)	0.0023 (7)	0.0000 (7)	0.0047 (8)

Geometric parameters (Å, °)

Cl1—C1	1.799 (2)	C2—C3	1.524 (3)
O1—C4	1.222 (2)	C2—H2A	0.9900
C5—C7	1.393 (2)	C2—H2B	0.9900
C5—C6	1.397 (3)	C1—H1A	0.9900
C5—N1	1.412 (2)	C1—H1B	0.9900
C6—C7i	1.381 (3)	C4—C3	1.505 (3)
C6—H6	0.9500	C3—H3A	0.9900
N1—C4	1.359 (2)	C3—H3B	0.9900
N1—H1	0.8800	C7—C6i	1.381 (3)
C2—C1	1.508 (3)	C7—H7	0.9500
C7—C5—C6	118.79 (17)	Cl1—C1—H1A	109.4
C7—C5—N1	123.01 (16)	C2—C1—H1B	109.4
C6—C5—N1	118.20 (16)	Cl1—C1—H1B	109.4
C7i—C6—C5	121.48 (17)	H1A—C1—H1B	108.0
C7i—C6—H6	119.3	O1—C4—N1	122.99 (17)
C5—C6—H6	119.3	O1—C4—C3	122.17 (16)
C4—N1—C5	126.45 (15)	N1—C4—C3	114.81 (15)
C4—N1—H1	116.8	C4—C3—C2	112.75 (15)
C5—N1—H1	116.8	C4—C3—H3A	109.0
C1—C2—C3	113.03 (16)	C2—C3—H3A	109.0
C1—C2—H2A	109.0	C4—C3—H3B	109.0
C3—C2—H2A	109.0	C2—C3—H3B	109.0
C1—C2—H2B	109.0	H3A—C3—H3B	107.8
C3—C2—H2B	109.0	C6i—C7—C5	119.73 (17)
H2A—C2—H2B	107.8	C6i—C7—H7	120.1
C2—C1—Cl1	111.34 (14)	C5—C7—H7	120.1
C2—C1—H1A	109.4
C7—C5—C6—C7i	0.1 (3)	C5—N1—C4—C3	171.72 (16)
N1—C5—C6—C7i	−179.67 (15)	O1—C4—C3—C2	−37.8 (2)
C7—C5—N1—C4	35.9 (3)	N1—C4—C3—C2	144.32 (17)
C6—C5—N1—C4	−144.38 (18)	C1—C2—C3—C4	−178.27 (15)
C3—C2—C1—Cl1	−67.01 (19)	C6—C5—C7—C6i	−0.1 (3)
C5—N1—C4—O1	−6.1 (3)	N1—C5—C7—C6i	179.66 (16)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ii	0.88	2.10	2.941 (3)	161

Symmetry codes: (ii) x−1, y, z.