Crystal structure of N,N′-(1,2-phenyl­ene)bis­(2-chloro­acetamide)

Tariq, J.; Murtaza, S.; Tahir, M.N.; Zaheer, M.

doi:10.1107/S2056989015000304

organic compounds

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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Page o108

doi:10.1107/S2056989015000304

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Crystal structure of N,N′-(1,2-phenylene)bis(2-chloroacetamide)

Javaria Tariq,^a Shahzad Murtaza,^a Muhammad Nawaz Tahir ^b ^* and Muhammad Zaheer ^a

^aDepartment of Chemistry, Institute of Chemical and Biological Sciences, University of Gujrat, Gujrat 50700, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Punjab, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 17 December 2014; accepted 7 January 2015; online 14 January 2015)

In the title compound, C₁₀H₁₀Cl₂N₂O₂, the secondary amide groups are differently twisted relative to the benzene ring, with dihedral angles between the respective planes of 21.03 (2) and 81.22 (2)°. In the crystal, the molecules are connected by N—H⋯O and C—H⋯O hydrogen bonds, forming a two-dimensional polymeric network parallel to (001). One of the amide carbonyl O atoms accepts two H atoms in N—H⋯O and C—H⋯O interactions, forming an R₂²(6) ring motif.

Keywords: crystal structure; 2-chloroacetamide; secondary amide groups; hydrogen bonding.

CCDC reference: 1042462

1. Related literature

For the structure of N,N′-phenylenebisacetamide, see: Shivanyuk et al. (2000 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₀Cl₂N₂O₂
M_r = 261.10
Monoclinic, P 2₁ /c
a = 4.5731 (4) Å
b = 14.3260 (16) Å
c = 16.7472 (15) Å
β = 95.611 (5)°
V = 1091.92 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 296 K
0.40 × 0.22 × 0.16 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.803, T_max = 0.911
8308 measured reflections
2154 independent reflections
1685 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.083
S = 1.03
2154 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.16	3.003 (2)	168
N2—H2⋯O1ⁱⁱ	0.86	2.23	3.004 (2)	150
C1—H1A⋯O2ⁱ	0.97	2.44	3.333 (3)	153
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON.

Supporting information

CCDC reference: 1042462

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015000304/gk2623sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000304/gk2623Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015000304/gk2623Isup3.cml

checkCIF report

Comment top

The title compound has been synthesized to check its antimicrobial activity owing to the concept that amide moiety is an important part of different drugs. The title molecule is shown in Fig. 1.

The benzene-1,2-diamine (C3—C8/N1/N2; A) unit is planar with r. m. s. deviation of 0.0084 Å. The attached chloroacetyl groups differ structurally. The groups B (C1/C2/O1) and C (C9/C10/O2) form with the fragment A the dihedral angles of 21.0 (2)° and 82.78 (13)°, respectively. The molecules are connected by N-H···O and C-H···O hydrogen bonds to form a two dimensional polymeric network parallel to (0 0 1) (Table 1, Fig. 2). In closely related N,N'-phenylenebisacetamide (Shivanyuk et al., 2000) a one dimensional ribbon is formed.

Related literature top

For the structure of N,N'-phenylenebisacetamide, see: Shivanyuk et al. (2000).

Experimental top

Benzene-1,2-diamine (0.1 g, 0.925 mmol) was dissolved in chloroform (10 ml) and pyridine (0.149 ml, 1.85 mmol) was added. The mixture was cooled to 273–278 K in ice-water bath. A separately prepared solution of chloroacetyl chloride (0.104 g, 0.925 mmol) in chloroform (5 ml) was added drop wise to the above mixture. The mixture was stirred for 3 h and solvent was evaporated to give a pink colored residue.Recrystallization from chloroform gave colorless needles with melting point of 471.15 K.

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: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Two dimensional polymeric network fomed via hydrogen bonds. The H-atoms not involved in hydrogen bonding are omitted for clarity.

N,N'-(1,2-Phenylene)bis(2-chloroacetamide) top

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	F(000) = 536
M_r = 261.10	D_x = 1.588 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.5731 (4) Å	Cell parameters from 1685 reflections
b = 14.3260 (16) Å	θ = 1.9–26.0°
c = 16.7472 (15) Å	µ = 0.58 mm⁻¹
β = 95.611 (5)°	T = 296 K
V = 1091.92 (18) Å³	Needle, colorless
Z = 4	0.40 × 0.22 × 0.16 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2154 independent reflections
Radiation source: fine-focus sealed tube	1685 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8.00 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→14
T_min = 0.803, T_max = 0.911	l = −20→20
8308 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0318P)² + 0.392P] where P = (F_o² + 2F_c²)/3
2154 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	V = 1091.92 (18) Å³
M_r = 261.10	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.5731 (4) Å	µ = 0.58 mm⁻¹
b = 14.3260 (16) Å	T = 296 K
c = 16.7472 (15) Å	0.40 × 0.22 × 0.16 mm
β = 95.611 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2154 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1685 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.911	R_int = 0.031
8308 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
2154 reflections	Δρ_min = −0.28 e Å⁻³
145 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	0.42275 (13)	0.31322 (5)	0.41502 (3)	0.0566 (2)
Cl2	1.17253 (12)	−0.12690 (5)	0.49132 (3)	0.05386 (19)
O1	0.5571 (3)	0.29789 (10)	0.23928 (9)	0.0451 (4)
O2	1.2396 (3)	0.00838 (11)	0.36111 (8)	0.0451 (4)
N1	0.5615 (3)	0.14134 (11)	0.26212 (9)	0.0310 (4)
H1	0.4935	0.0990	0.2917	0.037*
N2	0.8285 (3)	−0.03260 (11)	0.28396 (9)	0.0331 (4)
H2	0.6706	−0.0656	0.2809	0.040*
C1	0.2642 (4)	0.23927 (16)	0.33817 (13)	0.0420 (5)
H1A	0.2243	0.1785	0.3602	0.050*
H1B	0.0799	0.2655	0.3148	0.050*
C2	0.4749 (4)	0.22930 (14)	0.27444 (11)	0.0318 (4)
C3	0.7526 (4)	0.11071 (14)	0.20580 (10)	0.0297 (4)
C4	0.8061 (4)	0.16327 (16)	0.13895 (12)	0.0392 (5)
H4	0.7163	0.2211	0.1303	0.047*
C5	0.9919 (5)	0.12981 (17)	0.08557 (12)	0.0441 (5)
H5	1.0262	0.1653	0.0409	0.053*
C6	1.1271 (4)	0.04451 (17)	0.09760 (12)	0.0428 (5)
H6	1.2544	0.0228	0.0618	0.051*
C7	1.0726 (4)	−0.00838 (15)	0.16302 (12)	0.0382 (5)
H7	1.1621	−0.0664	0.1711	0.046*
C8	0.8855 (4)	0.02408 (14)	0.21689 (11)	0.0301 (4)
C9	1.0116 (4)	−0.03627 (13)	0.35130 (11)	0.0314 (4)
C10	0.8997 (4)	−0.09830 (17)	0.41444 (13)	0.0451 (5)
H10A	0.8221	−0.1553	0.3893	0.054*
H10B	0.7399	−0.0669	0.4375	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0649 (4)	0.0620 (5)	0.0442 (3)	−0.0031 (3)	0.0113 (3)	−0.0083 (3)
Cl2	0.0561 (4)	0.0613 (4)	0.0443 (3)	0.0051 (3)	0.0057 (2)	0.0141 (3)
O1	0.0551 (9)	0.0273 (9)	0.0557 (9)	0.0023 (6)	0.0198 (7)	0.0054 (7)
O2	0.0390 (8)	0.0483 (10)	0.0478 (8)	−0.0158 (7)	0.0025 (6)	0.0089 (7)
N1	0.0331 (8)	0.0248 (10)	0.0368 (8)	−0.0025 (6)	0.0114 (7)	0.0037 (7)
N2	0.0272 (8)	0.0277 (9)	0.0448 (9)	−0.0047 (6)	0.0055 (7)	0.0056 (8)
C1	0.0354 (11)	0.0351 (13)	0.0574 (13)	−0.0016 (9)	0.0148 (9)	−0.0049 (11)
C2	0.0274 (9)	0.0287 (12)	0.0395 (10)	−0.0006 (8)	0.0040 (8)	0.0006 (9)
C3	0.0268 (9)	0.0299 (11)	0.0327 (9)	−0.0042 (8)	0.0052 (7)	−0.0024 (9)
C4	0.0439 (11)	0.0360 (13)	0.0389 (10)	0.0029 (9)	0.0106 (9)	0.0069 (10)
C5	0.0498 (13)	0.0494 (15)	0.0347 (10)	−0.0058 (11)	0.0122 (9)	0.0042 (10)
C6	0.0425 (12)	0.0494 (15)	0.0385 (11)	−0.0029 (10)	0.0139 (9)	−0.0100 (11)
C7	0.0351 (10)	0.0318 (12)	0.0484 (12)	0.0002 (9)	0.0071 (9)	−0.0068 (10)
C8	0.0269 (9)	0.0289 (11)	0.0345 (9)	−0.0055 (8)	0.0024 (8)	−0.0005 (9)
C9	0.0300 (10)	0.0237 (11)	0.0420 (10)	0.0011 (8)	0.0102 (8)	0.0015 (9)
C10	0.0410 (12)	0.0434 (14)	0.0507 (12)	−0.0061 (10)	0.0046 (10)	0.0123 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.767 (2)	C3—C8	1.387 (3)
Cl2—C10	1.752 (2)	C3—C4	1.391 (3)
O1—C2	1.223 (2)	C4—C5	1.378 (3)
O2—C9	1.221 (2)	C4—H4	0.9300
N1—C2	1.343 (2)	C5—C6	1.375 (3)
N1—C3	1.417 (2)	C5—H5	0.9300
N1—H1	0.8600	C6—C7	1.375 (3)
N2—C9	1.338 (2)	C6—H6	0.9300
N2—C8	1.431 (2)	C7—C8	1.383 (3)
N2—H2	0.8600	C7—H7	0.9300
C1—C2	1.513 (3)	C9—C10	1.509 (3)
C1—H1A	0.9700	C10—H10A	0.9700
C1—H1B	0.9700	C10—H10B	0.9700

C2—N1—C3	127.11 (16)	C6—C5—C4	120.71 (19)
C2—N1—H1	116.4	C6—C5—H5	119.6
C3—N1—H1	116.4	C4—C5—H5	119.6
C9—N2—C8	122.45 (15)	C7—C6—C5	119.51 (19)
C9—N2—H2	118.8	C7—C6—H6	120.2
C8—N2—H2	118.8	C5—C6—H6	120.2
C2—C1—Cl1	109.02 (14)	C6—C7—C8	120.4 (2)
C2—C1—H1A	109.9	C6—C7—H7	119.8
Cl1—C1—H1A	109.9	C8—C7—H7	119.8
C2—C1—H1B	109.9	C7—C8—C3	120.32 (18)
Cl1—C1—H1B	109.9	C7—C8—N2	119.55 (18)
H1A—C1—H1B	108.3	C3—C8—N2	120.13 (16)
O1—C2—N1	124.80 (17)	O2—C9—N2	123.29 (18)
O1—C2—C1	120.69 (19)	O2—C9—C10	123.94 (17)
N1—C2—C1	114.50 (17)	N2—C9—C10	112.73 (16)
C8—C3—C4	118.89 (17)	C9—C10—Cl2	112.76 (14)
C8—C3—N1	118.63 (16)	C9—C10—H10A	109.0
C4—C3—N1	122.47 (18)	Cl2—C10—H10A	109.0
C5—C4—C3	120.1 (2)	C9—C10—H10B	109.0
C5—C4—H4	119.9	Cl2—C10—H10B	109.0
C3—C4—H4	119.9	H10A—C10—H10B	107.8

C3—N1—C2—O1	−2.1 (3)	C6—C7—C8—N2	179.12 (17)
C3—N1—C2—C1	178.87 (16)	C4—C3—C8—C7	1.2 (3)
Cl1—C1—C2—O1	−58.8 (2)	N1—C3—C8—C7	179.76 (16)
Cl1—C1—C2—N1	120.23 (16)	C4—C3—C8—N2	−178.35 (17)
C2—N1—C3—C8	161.13 (17)	N1—C3—C8—N2	0.2 (2)
C2—N1—C3—C4	−20.4 (3)	C9—N2—C8—C7	81.8 (2)
C8—C3—C4—C5	−0.9 (3)	C9—N2—C8—C3	−98.6 (2)
N1—C3—C4—C5	−179.38 (18)	C8—N2—C9—O2	0.4 (3)
C3—C4—C5—C6	−0.2 (3)	C8—N2—C9—C10	178.10 (17)
C4—C5—C6—C7	0.9 (3)	O2—C9—C10—Cl2	−17.4 (3)
C5—C6—C7—C8	−0.6 (3)	N2—C9—C10—Cl2	164.89 (15)
C6—C7—C8—C3	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.16	3.003 (2)	168
N2—H2···O1ⁱⁱ	0.86	2.23	3.004 (2)	150
C1—H1A···O2ⁱ	0.97	2.44	3.333 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.16	3.003 (2)	168
N2—H2···O1ⁱⁱ	0.86	2.23	3.004 (2)	150
C1—H1A···O2ⁱ	0.97	2.44	3.333 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. They also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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