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

Cuzan, O.; Shova, S.; Turta, C.; Mangalagiu, I.I.

doi:10.1107/S1600536812001341

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o463

doi:10.1107/S1600536812001341

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

Olesea Cuzan,^a ^* Sergiu Shova,^b,^c Constantin Turta ^a and Ionel I. Mangalagiu ^d

^aInstitute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei Street, Chisinau MD-2028, Moldova, ^bInstitute of Applied Physics of the Academy of Science of Moldova, 5 Academiei Street, Chisinau MD-2028, Moldova, ^cInstitute of Macromolecular Chemistry "Petru Poni", 41A Grigore Ghica Voda Alley, Iasi-700487, Romania, and ^d"Alexandru Ioan Cuza" University, Organic Chemistry Department, 11 Carol I Boulevard, Iasi-700506, Romania
^*Correspondence e-mail: olesea_cuzan@yahoo.com

(Received 25 November 2011; accepted 11 January 2012; online 18 January 2012)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.038
wR(F²) = 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

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) x-1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001341/nk2130sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001341/nk2130Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812001341/nk2130Isup3.cml

checkCIF report

Comment top

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°.

Related literature top

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 top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 (Sheldrick, 2008).

Figures top

	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.

N,N'-(1,4-Phenylene)bis(4-chlorobutanamide) top

Crystal data top

C₁₄H₁₈Cl₂N₂O₂	Z = 1
M_r = 317.20	F(000) = 166
Triclinic, P1	D_x = 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 top

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

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0387P)² + 0.0691P] where P = (F_o² + 2F_c²)/3
1446 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₄H₁₈Cl₂N₂O₂	γ = 90.512 (5)°
M_r = 317.20	V = 366.3 (5) Å³
Triclinic, P1	Z = 1
a = 5.105 (5) Å	Mo Kα radiation
b = 6.876 (5) Å	µ = 0.45 mm⁻¹
c = 10.549 (5) Å	T = 200 K
α = 97.735 (5)°	0.25 × 0.2 × 0.2 mm
β = 93.214 (5)°

Data collection top

Agilent Xcalibur Eos diffractometer	1446 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1189 reflections with I > 2σ(I)
T_min = 0.914, T_max = 1.000	R_int = 0.026
2575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
1446 reflections	Δρ_min = −0.26 e Å⁻³
91 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
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 (Å²) top

	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, º) top

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 code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈Cl₂N₂O₂
M_r	317.20
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	5.105 (5), 6.876 (5), 10.549 (5)
α, β, γ (°)	97.735 (5), 93.214 (5), 90.512 (5)
V (Å³)	366.3 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.25 × 0.2 × 0.2

Data collection
Diffractometer	Agilent Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.914, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2575, 1446, 1189
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.092, 1.03
No. of reflections	1446
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.26

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.10	2.941 (3)	160.9

Symmetry code: (i) x−1, y, z.

Acknowledgements

This research was supported by PCAP FP7-PEOPLE-2009-IRSES (No. 246902) and the Development Fund, Sectoral Operational Programme "Increase of Economic Competitiveness", Priority Axis 2 (SOP IEC-A2-O2.1.2-2009-2, ID 570, COD SMIS-CSNR: 12473, Contract 129/2010-POLISILMET).

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