Diethyl N,N′-(p-phenylene)dioxamate

Yang, W.; Liu, X.

doi:10.1107/S1600536808027190

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1852

doi:10.1107/S1600536808027190

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Diethyl N,N′-(p-phenylene)dioxamate

Wei Yang ^a and Xiaoyu Liu ^a,^b ^*

^aSchool of Life Sciences, Northeast Normal University, Changchun 130024, People's Republic of China, and ^bCollege of Sciences, Shenyang Agricultural University, Shenyang 110161, People's Republic of China
^*Correspondence e-mail: liuxiaoyu126@yahoo.cn

(Received 19 August 2008; accepted 23 August 2008; online 30 August 2008)

In the crystal structure, the molecule of the title compound, C₁₄H₁₆N₂O₆, is located on an inversion centre. The amide –NHCO– plane makes a dihedral angle of 34.08 (9)° with the benzene ring. The molecules are connected via intermolecular O—H⋯N hydrogen bonds into a two-dimensional network parallel to the bc plane. An intramolecular N—H⋯O hydrogen bond is also observed.

Related literature

For related literature, see: Hashmi et al. (2004 ); Navarro et al. (1998 ); Nonoyama et al. (1982 ); Pardo et al. (2003 ); Rios-Moreno et al. (2003 ).

Experimental

Crystal data

C₁₄H₁₆N₂O₆
M_r = 308.29
Monoclinic, P 2₁ /c
a = 11.328 (5) Å
b = 7.769 (5) Å
c = 8.372 (5) Å
β = 95.566 (5)°
V = 733.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 (2) K
0.3 × 0.2 × 0.1 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.975, T_max = 0.989
5037 measured reflections
1285 independent reflections
1075 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.136
S = 1.00
1285 reflections
104 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.85 (2)	2.30 (2)	2.701 (3)	109.0 (19)
N1—H1N⋯O3ⁱ	0.85 (2)	2.21 (3)	3.030 (3)	161 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027190/is2327sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027190/is2327Isup2.hkl

checkCIF report

Comment top

Oxamido ligands were extensively investigated owing to their special biological properties and application prospects (Nonoyama et al., 1982). However, the ligands of oxalamic acid ethyl ester were rarely reported, in which ester group can stabilize the final compounds by producing complexes with main group and transition metals (Rios-Moreno et al., 2003). In this work, the title compound, (I), was characterized by XRD single-crystal diffraction, element analysis and IR.

In the molecule (Fig. 1), the bond lengths containing O and N atoms are all consistent with corresponding values observed in similar systems (Navarro et al., 1998; Hashmi et al., 2004). There exists an intermolecular hydrogen bond involving the carboxamide O atom and the carboxamide N atom with a distance of 3.030 (3) Å, which are in agreement with those found in related compounds. Simultaneously, the molecule units are assembled into two dimensional structure with the intermolecular hydrogen-bond interactions.

Related literature top

For related literature, see: Hashmi et al. (2004); Navarro et al. (1998); Nonoyama et al. (1982); Pardo et al. (2003); Rios-Moreno et al. (2003).

Experimental top

The synthesis method of the title compound is according to the previous literature method (Pardo et al., 2003). Colorless single crystals suitable for experiments were obtained from a methanol solution. Elemental analysis calculated for C₁₄H₁₆N₂O₆: C 54.54, H 5.23, N 9.09%; found C 54.52, H 5.22, N 9.08%. IR data: 3249 cm^-1 (m, N—H), 1682 cm^-1 (s, C=O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the unique atom-labelling scheme. The suffix A corresponds to symmetry code (-x + 2, -y, -z + 2). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The hydrogen-bonded network in (I). Hydrogen bonds are indicated by dashed lines. All H atoms except the H atoms of imido N atoms have been omitted for clarity.

Diethyl N,N'-(p-phenylene)dioxamate top

Crystal data top

C₁₄H₁₆N₂O₆	F(000) = 324
M_r = 308.29	D_x = 1.396 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2859 reflections
a = 11.328 (5) Å	θ = 2.2–27.0°
b = 7.769 (5) Å	µ = 0.11 mm⁻¹
c = 8.372 (5) Å	T = 295 K
β = 95.566 (5)°	Sheet, colorless
V = 733.3 (7) Å³	0.3 × 0.2 × 0.1 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1285 independent reflections
Radiation source: fine-focus sealed tube	1075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→13
T_min = 0.975, T_max = 0.989	k = −9→8
5037 measured reflections	l = −9→9

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0715P)² + 0.3357P] where P = (F_o² + 2F_c²)/3
1285 reflections	(Δ/σ)_max = 0.022
104 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₆N₂O₆	V = 733.3 (7) Å³
M_r = 308.29	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.328 (5) Å	µ = 0.11 mm⁻¹
b = 7.769 (5) Å	T = 295 K
c = 8.372 (5) Å	0.3 × 0.2 × 0.1 mm
β = 95.566 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1285 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1075 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.989	R_int = 0.017
5037 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.33 e Å⁻³
1285 reflections	Δρ_min = −0.19 e Å⁻³
104 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
O1	0.70158 (18)	0.6118 (2)	0.73921 (19)	0.0770 (6)
O2	0.68604 (16)	0.3705 (2)	0.59603 (19)	0.0759 (6)
O3	0.82720 (14)	0.44460 (17)	0.97740 (16)	0.0564 (5)
N1	0.84872 (15)	0.2185 (2)	0.8077 (2)	0.0475 (5)
H1N	0.826 (2)	0.183 (3)	0.714 (3)	0.058 (6)*
C1	0.92637 (16)	0.1107 (2)	0.9062 (2)	0.0433 (5)
C2	0.91424 (18)	−0.0652 (3)	0.8901 (2)	0.0530 (5)
H2	0.8563	−0.1096	0.8150	0.064*
C3	1.01346 (18)	0.1763 (3)	1.0168 (2)	0.0515 (5)
H3	1.0232	0.2947	1.0282	0.062*
C4	0.80684 (17)	0.3714 (2)	0.8486 (2)	0.0443 (5)
C5	0.72433 (18)	0.4498 (3)	0.7117 (2)	0.0503 (5)
C6	0.6271 (4)	0.7022 (4)	0.6127 (4)	0.1143 (14)
H6A	0.6762	0.7417	0.5314	0.137*
H6B	0.5689	0.6227	0.5622	0.137*
C7	0.5702 (4)	0.8389 (6)	0.6711 (5)	0.1472 (19)
H7A	0.5245	0.8966	0.5846	0.221*
H7B	0.6275	0.9172	0.7224	0.221*
H7C	0.5185	0.7995	0.7478	0.221*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1129 (14)	0.0571 (10)	0.0539 (9)	0.0175 (9)	−0.0278 (9)	0.0023 (8)
O2	0.0842 (12)	0.0826 (12)	0.0549 (10)	0.0192 (9)	−0.0235 (9)	−0.0186 (9)
O3	0.0795 (10)	0.0479 (8)	0.0392 (8)	0.0048 (7)	−0.0080 (7)	−0.0032 (6)
N1	0.0564 (10)	0.0515 (10)	0.0332 (9)	0.0021 (7)	−0.0034 (7)	−0.0044 (7)
C1	0.0476 (10)	0.0482 (11)	0.0338 (9)	0.0006 (8)	0.0026 (8)	−0.0021 (8)
C2	0.0536 (11)	0.0516 (12)	0.0507 (12)	−0.0030 (9)	−0.0110 (9)	−0.0099 (9)
C3	0.0556 (11)	0.0422 (11)	0.0545 (12)	−0.0030 (9)	−0.0054 (9)	−0.0054 (9)
C4	0.0523 (10)	0.0454 (10)	0.0346 (10)	−0.0041 (8)	0.0012 (8)	0.0024 (8)
C5	0.0558 (11)	0.0541 (12)	0.0400 (11)	0.0022 (9)	0.0000 (9)	−0.0005 (9)
C6	0.176 (4)	0.089 (2)	0.0665 (17)	0.046 (2)	−0.047 (2)	0.0065 (16)
C7	0.162 (4)	0.172 (4)	0.102 (3)	0.092 (3)	−0.017 (3)	0.032 (3)

Geometric parameters (Å, º) top

O1—C5	1.310 (3)	C2—H2	0.9300
O1—C6	1.467 (3)	C3—C2ⁱ	1.379 (3)
O2—C5	1.193 (2)	C3—H3	0.9300
O3—C4	1.221 (2)	C4—C5	1.533 (3)
N1—C4	1.336 (3)	C6—C7	1.358 (5)
N1—C1	1.419 (2)	C6—H6A	0.9700
N1—H1N	0.85 (2)	C6—H6B	0.9700
C1—C2	1.379 (3)	C7—H7A	0.9600
C1—C3	1.383 (3)	C7—H7B	0.9600
C2—C3ⁱ	1.379 (3)	C7—H7C	0.9600

C4—N1—C1	126.25 (17)	C7—C6—O1	111.9 (3)
C4—N1—H1N	116.1 (15)	C7—C6—H6A	109.2
C1—N1—H1N	117.6 (15)	O1—C6—H6A	109.2
C5—O1—C6	116.2 (2)	C7—C6—H6B	109.2
O3—C4—N1	126.80 (18)	O1—C6—H6B	109.2
O3—C4—C5	121.63 (18)	H6A—C6—H6B	107.9
N1—C4—C5	111.56 (16)	C1—C2—C3ⁱ	121.15 (19)
C2—C1—C3	119.26 (18)	C1—C2—H2	119.4
C2—C1—N1	118.55 (17)	C3ⁱ—C2—H2	119.4
C3—C1—N1	122.19 (18)	C6—C7—H7A	109.5
O2—C5—O1	125.2 (2)	C6—C7—H7B	109.5
O2—C5—C4	123.3 (2)	H7A—C7—H7B	109.5
O1—C5—C4	111.49 (17)	C6—C7—H7C	109.5
C2ⁱ—C3—C1	119.58 (19)	H7A—C7—H7C	109.5
C2ⁱ—C3—H3	120.2	H7B—C7—H7C	109.5
C1—C3—H3	120.2

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.85 (2)	2.30 (2)	2.701 (3)	109.0 (19)
N1—H1N···O3ⁱⁱ	0.85 (2)	2.21 (3)	3.030 (3)	161 (2)

Symmetry code: (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂O₆
M_r	308.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	11.328 (5), 7.769 (5), 8.372 (5)
β (°)	95.566 (5)
V (Å³)	733.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.975, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	5037, 1285, 1075
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.136, 1.00
No. of reflections	1285
No. of parameters	104
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.19

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.85 (2)	2.30 (2)	2.701 (3)	109.0 (19)
N1—H1N···O3ⁱ	0.85 (2)	2.21 (3)	3.030 (3)	161 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

We thank the Analysis and Testing Foundation of Northeast Normal University for financial support.

References

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