N,N′-Bis(2,5-dichloro­phen­yl)isophthalamide

Zhu, R.; Dong, J.; Zuo, Y.; Ren, Y.

doi:10.1107/S1600536811031758

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2311

doi:10.1107/S1600536811031758

Open

access

N,N′-Bis(2,5-dichlorophenyl)isophthalamide

Ruitao Zhu,^a Jinlong Dong,^a Yu Zuo ^a and Yuehong Ren ^a ^*

^aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: ruitaozhu@126.com

(Received 19 July 2011; accepted 5 August 2011; online 11 August 2011)

The asymmetric unit of the title compound, C₂₀H₁₂Cl₄N₂O₂, contains one half-molecule with a center of symmetry along a C⋯C axis of the central benzene ring. The two C=O groups adopt an anti orientation and the two amide groups are twisted away from the central benzene ring by 27.38 (3) and 27.62 (4)°. The mean planes of the dichloro-substituted benzene rings are twisted by 7.95 (4)° with respect to the benzene ring. The crystal packing is stabilized by weak intermolecular N—H⋯O interactions.

Related literature

For the design of artificial receptors related to isophthalamide, see: Gale (2006 ). For related structures, see: Light et al. (2006 ); Kavallieratos et al. (1997 , 1999 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₁₂Cl₄N₂O₂
M_r = 454.12
Monoclinic, P 2/c
a = 11.3661 (11) Å
b = 10.0239 (9) Å
c = 8.9470 (7) Å
β = 109.988 (1)°
V = 957.95 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 298 K
0.49 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.745, T_max = 0.939
4668 measured reflections
1687 independent reflections
1152 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.110
S = 1.01
1687 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.22	3.046 (3)	160
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (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) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031758/jj2095sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031758/jj2095Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811031758/jj2095Isup3.cml

checkCIF report

Comment top

Anion recognition is an area of growing interest in supramolecular chemistry due to its important role in a wide range of environmental, clinical, chemical, and biological applications. Considerable attention has been focused on the design of artificial receptors that are able to selectively recognize and sense anion species (Gale, 2006). Artificial receptors, containing the isophthalamide core function as effective receptors for halide anions in very simple systems (Kavallieratos et al., 1997, 1999; Light et al. 2006). We report here the crystal structure of the title compound, C₂₀H₁₂Cl₄N₂O₂, (I), related to these types of receptors.

In the title compound,(I), the asymmetric unit containing one-half of the molecule crystallizes with a center of symmetry along the C2—C5 axis in the benzene ring thereby producing the desired structure (Fig. 1). In the molecule the two C═O groups adopt an anti orientation and the two amide groups are twisted away from the center benzene ring by 27.38 (3) ° and 27.62 (4) °, respectively. The mean planes of the dichloro substituted benzene rings are twisted by 7.95 (4) ° with that of the benzene ring. Bond lengths are in normal ranges (Allen et al., 1987). Crystal packing is stabilized by weak N—H···O intermolecular interactions (Table 1).

Related literature top

For the design of artificial receptors related to isophthalamide, see: Gale (2006). For related structures, see: Light et al. (2006); Kavallieratos et al. (1997, 1999). For standard bond lengths, see: Allen et al. (1987).

Experimental top

N,N-Bis(2,5-dichlorophenyl)isophthalamide (I) was prepared according to literature procedures (Kavallieratos et al., 1997, 1999). To dichloromethane (20 ml) in a 100 ml flask was added 2,5-dichloroaniline(1.62 g, 10 mmol) with magnetic stirring. Isophthalogyl chloride (1.01 g, 5 mmol) was added gradually, and the reaction mixture was stirred at room temperature for 2 h and then poured into ice water (100 ml). The product was precipitated as a white powder, which was washed three times with water. Recrystallization from dimethyl sulfoxide solution produced the crystals of the title compound.

Computing details top

Data collection: SMART (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) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids are drawn at the 30% probability level.

N,N'-bis(2,5-dichlorophenyl)benzene-1,3-dicarboxamide top

Crystal data top

C₂₀H₁₂Cl₄N₂O₂	F(000) = 460
M_r = 454.12	D_x = 1.574 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 1505 reflections
a = 11.3661 (11) Å	θ = 2.8–27.4°
b = 10.0239 (9) Å	µ = 0.64 mm⁻¹
c = 8.9470 (7) Å	T = 298 K
β = 109.988 (1)°	Prism, colorless
V = 957.95 (15) Å³	0.49 × 0.20 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1687 independent reflections
Radiation source: fine-focus sealed tube	1152 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→6
T_min = 0.745, T_max = 0.939	k = −11→11
4668 measured reflections	l = −10→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0416P)² + 0.6846P] where P = (F_o² + 2F_c²)/3
1687 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂₀H₁₂Cl₄N₂O₂	V = 957.95 (15) Å³
M_r = 454.12	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 11.3661 (11) Å	µ = 0.64 mm⁻¹
b = 10.0239 (9) Å	T = 298 K
c = 8.9470 (7) Å	0.49 × 0.20 × 0.10 mm
β = 109.988 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1687 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1152 reflections with I > 2σ(I)
T_min = 0.745, T_max = 0.939	R_int = 0.030
4668 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	Δρ_max = 0.27 e Å⁻³
1687 reflections	Δρ_min = −0.30 e Å⁻³
128 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	0.64968 (9)	0.85140 (8)	0.38003 (10)	0.0726 (3)
Cl2	0.99324 (10)	0.70144 (15)	1.06068 (10)	0.1021 (5)
N1	0.7062 (2)	0.5769 (2)	0.4952 (2)	0.0412 (6)
H1	0.6911	0.5986	0.3974	0.049*
O1	0.70204 (19)	0.4014 (2)	0.6539 (2)	0.0544 (6)
C1	0.6692 (2)	0.4532 (3)	0.5224 (3)	0.0392 (7)
C2	0.5000	0.4520 (4)	0.2500	0.0362 (9)
H2	0.5000	0.5448	0.2500	0.043*
C3	0.5811 (2)	0.3842 (3)	0.3794 (3)	0.0372 (6)
C4	0.5787 (3)	0.2456 (3)	0.3786 (4)	0.0537 (8)
H4	0.6306	0.1985	0.4657	0.064*
C5	0.5000	0.1782 (4)	0.2500	0.0638 (13)
H5	0.5000	0.0854	0.2500	0.077*
C6	0.7666 (2)	0.6736 (3)	0.6099 (3)	0.0401 (7)
C7	0.7463 (3)	0.8080 (3)	0.5689 (3)	0.0489 (8)
C8	0.8009 (3)	0.9072 (4)	0.6768 (4)	0.0672 (10)
H8	0.7873	0.9962	0.6468	0.081*
C9	0.8753 (3)	0.8746 (4)	0.8289 (4)	0.0732 (11)
H9	0.9104	0.9410	0.9034	0.088*
C10	0.8969 (3)	0.7431 (4)	0.8689 (4)	0.0640 (10)
C11	0.8451 (3)	0.6423 (3)	0.7628 (3)	0.0513 (8)
H11	0.8624	0.5536	0.7932	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0832 (7)	0.0488 (5)	0.0643 (6)	0.0049 (4)	−0.0025 (5)	0.0043 (4)
Cl2	0.0748 (7)	0.1852 (13)	0.0349 (5)	−0.0308 (7)	0.0039 (4)	−0.0066 (6)
N1	0.0485 (14)	0.0452 (14)	0.0276 (11)	−0.0025 (11)	0.0101 (10)	0.0034 (10)
O1	0.0655 (14)	0.0594 (13)	0.0382 (11)	0.0103 (11)	0.0177 (10)	0.0161 (10)
C1	0.0390 (15)	0.0439 (16)	0.0397 (16)	0.0121 (13)	0.0197 (13)	0.0064 (13)
C2	0.041 (2)	0.0292 (19)	0.042 (2)	0.000	0.0197 (18)	0.000
C3	0.0366 (15)	0.0367 (15)	0.0427 (16)	0.0029 (12)	0.0191 (13)	0.0041 (12)
C4	0.0489 (18)	0.0418 (17)	0.069 (2)	0.0079 (15)	0.0184 (16)	0.0109 (15)
C5	0.069 (3)	0.027 (2)	0.089 (4)	0.000	0.019 (3)	0.000
C6	0.0347 (15)	0.0546 (18)	0.0327 (15)	−0.0042 (13)	0.0139 (12)	−0.0040 (13)
C7	0.0422 (17)	0.0531 (18)	0.0475 (17)	−0.0007 (14)	0.0101 (14)	−0.0103 (14)
C8	0.061 (2)	0.064 (2)	0.075 (2)	−0.0116 (18)	0.020 (2)	−0.0223 (19)
C9	0.056 (2)	0.102 (3)	0.061 (2)	−0.020 (2)	0.0185 (19)	−0.040 (2)
C10	0.0418 (18)	0.115 (3)	0.0355 (17)	−0.016 (2)	0.0131 (14)	−0.0138 (19)
C11	0.0395 (16)	0.077 (2)	0.0369 (16)	−0.0049 (16)	0.0128 (14)	0.0011 (16)

Geometric parameters (Å, º) top

Cl1—C7	1.727 (3)	C4—H4	0.9300
Cl2—C10	1.742 (3)	C5—C4ⁱ	1.370 (4)
N1—C1	1.358 (3)	C5—H5	0.9300
N1—C6	1.408 (3)	C6—C11	1.390 (4)
N1—H1	0.8600	C6—C7	1.395 (4)
O1—C1	1.222 (3)	C7—C8	1.376 (4)
C1—C3	1.498 (4)	C8—C9	1.373 (5)
C2—C3ⁱ	1.387 (3)	C8—H8	0.9300
C2—C3	1.387 (3)	C9—C10	1.366 (5)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.389 (4)	C10—C11	1.374 (5)
C4—C5	1.370 (4)	C11—H11	0.9300

C1—N1—C6	127.0 (2)	C11—C6—C7	118.0 (3)
C1—N1—H1	116.5	C11—C6—N1	123.5 (3)
C6—N1—H1	116.5	C7—C6—N1	118.5 (2)
O1—C1—N1	123.3 (3)	C8—C7—C6	121.2 (3)
O1—C1—C3	121.4 (3)	C8—C7—Cl1	119.2 (3)
N1—C1—C3	115.2 (2)	C6—C7—Cl1	119.6 (2)
C3ⁱ—C2—C3	121.2 (3)	C9—C8—C7	120.0 (3)
C3ⁱ—C2—H2	119.4	C9—C8—H8	120.0
C3—C2—H2	119.4	C7—C8—H8	120.0
C2—C3—C4	118.7 (3)	C10—C9—C8	118.9 (3)
C2—C3—C1	123.1 (2)	C10—C9—H9	120.5
C4—C3—C1	118.2 (2)	C8—C9—H9	120.5
C5—C4—C3	120.2 (3)	C9—C10—C11	122.2 (3)
C5—C4—H4	119.9	C9—C10—Cl2	119.1 (3)
C3—C4—H4	119.9	C11—C10—Cl2	118.7 (3)
C4—C5—C4ⁱ	120.9 (4)	C10—C11—C6	119.5 (3)
C4—C5—H5	119.6	C10—C11—H11	120.2
C4ⁱ—C5—H5	119.6	C6—C11—H11	120.2

C6—N1—C1—O1	−12.3 (4)	C11—C6—C7—C8	−0.8 (5)
C6—N1—C1—C3	166.2 (2)	N1—C6—C7—C8	178.8 (3)
C3ⁱ—C2—C3—C4	−0.9 (2)	C11—C6—C7—Cl1	179.9 (2)
C3ⁱ—C2—C3—C1	−179.2 (3)	N1—C6—C7—Cl1	−0.6 (4)
O1—C1—C3—C2	151.0 (2)	C6—C7—C8—C9	−1.0 (5)
N1—C1—C3—C2	−27.5 (3)	Cl1—C7—C8—C9	178.3 (3)
O1—C1—C3—C4	−27.4 (4)	C7—C8—C9—C10	2.0 (5)
N1—C1—C3—C4	154.2 (3)	C8—C9—C10—C11	−1.1 (6)
C2—C3—C4—C5	1.9 (4)	C8—C9—C10—Cl2	179.0 (3)
C1—C3—C4—C5	−179.7 (2)	C9—C10—C11—C6	−0.8 (5)
C3—C4—C5—C4ⁱ	−1.0 (2)	Cl2—C10—C11—C6	179.1 (2)
C1—N1—C6—C11	29.4 (4)	C7—C6—C11—C10	1.7 (4)
C1—N1—C6—C7	−150.1 (3)	N1—C6—C11—C10	−177.8 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.86	2.22	3.046 (3)	160

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₂Cl₄N₂O₂
M_r	454.12
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	298
a, b, c (Å)	11.3661 (11), 10.0239 (9), 8.9470 (7)
β (°)	109.988 (1)
V (Å³)	957.95 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.49 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.745, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	4668, 1687, 1152
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.110, 1.01
No. of reflections	1687
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.30

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.224	3.046 (3)	159.75

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

The authors gratefully acknowledge the University Technology Development Project in Shanxi Province (grant Nos. 20091144, 20101116).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gale, P. A. (2006). Acc. Chem. Res. 36, 465–475. CrossRef Google Scholar
Kavallieratos, K., Bertao, C. M. & Grabtee, R. H. (1999). J. Org. Chem. 64, 1675–1683. CrossRef CAS Google Scholar
Kavallieratos, K., Gala, S. R., Austin, D. J. & Grabtee, R. H. (1997). J. Am. Chem. Soc. 119, 2325–2326. CrossRef CAS Google Scholar
Light, M. E., Gale, P. A. & Navakhun, K. (2006). Acta Cryst. E62, o1097–o1098. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar