N,N′-Bis(2-hydroxy­ethyl)benzene-1,4-dicarboxamide

Bednarek, G.; Kusz, J.; Ratuszna, A.; Ossowski, J.; Sułkowski, W.W.

doi:10.1107/S1600536808017467

organic compounds

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Volume 64| Part 7| July 2008| Page o1277

doi:10.1107/S1600536808017467

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N,N′-Bis(2-hydroxyethyl)benzene-1,4-dicarboxamide

Gabriela Bednarek,^a ^* Joachim Kusz,^a Alicja Ratuszna,^a Jerzy Ossowski ^b and Wiesław W. Sułkowski ^b

^aInstitute of Physics, University of Silesia, 40-007 Katowice, Poland, and ^bDepartment of Environmental Chemistry and Technology, Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
^*Correspondence e-mail: gbednare@us.edu.pl

(Received 20 May 2008; accepted 10 June 2008; online 19 June 2008)

The molecule of the title compound, C₁₂H₁₆N₂O₄, is centrosymmetric and the amide group is twisted relative to the benzene ring by 14.40 (13)°. The molecules are hydrogen bonded into a three-dimensional framework, with the hydroxy O atoms acting as acceptors in N—H⋯O hydrogen bonds and as donors in O—H⋯O=C interactions.

Related literature

For the synthesis of the title compound, see: Sułkowski et al. (2000 ); Shukla & Harad (2006 ). For bond-length data, see: Allen (2002 ). For hydrogen bonding, see: Desiraju & Steiner (1999 ).

Experimental

Crystal data

C₁₂H₁₆N₂O₄
M_r = 252.27
Monoclinic, P 2₁ /c
a = 4.9062 (4) Å
b = 13.6467 (10) Å
c = 8.8840 (7) Å
β = 97.262 (6)°
V = 590.04 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 200 (1) K
0.26 × 0.22 × 0.18 mm

Data collection

Oxford Diffraction KM-4-CCD Sapphire3 diffractometer
Absorption correction: none
5655 measured reflections
2000 independent reflections
1599 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.097
S = 1.02
2000 reflections
114 parameters
All H-atom parameters refined
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H3⋯O2ⁱ	0.879 (16)	2.080 (16)	2.9333 (10)	163.3 (13)
O2—H8⋯O1ⁱⁱ	0.863 (18)	1.872 (18)	2.7204 (9)	167.1 (15)
C2—H2⋯O2ⁱ	0.972 (15)	2.412 (14)	3.3458 (11)	161.0 (11)
C5—H4⋯O1ⁱⁱ	0.988 (12)	2.523 (12)	3.2738 (12)	132.6 (9)
C5—H5⋯O1ⁱⁱⁱ	0.992 (13)	2.612 (13)	3.5671 (12)	161.7 (11)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017467/gk2148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017467/gk2148Isup2.hkl

checkCIF report

Comment top

Polyethylene terephthalate (PET) is a very popular thermoplastic polyester. The chemical recycling of its wastes has been the subject of keen interest as a valuable material for different chemical processes. Aminolysis of PET yields N, N' - bis(2-hydroxyethyl)benzene-1,4-dicarboxamide, which can be a potential candidate for further reactions leading to obtain other useful products. To get information about the hydrogen bonding in this interesting material we determined its crystal structure. In crystal the title molecule is located around inversion center (Fig. 1.).

The value of the C2—C3—C4 angle of 123.58 (7)° is in agreement with a geometry of the Ph—C(=O)—NH—CH₂subunit. A search of the Cambridge Structural Database [version 5.28; Allen, 2002] shows that in similar compounds this angle is consistently greater than 120° with the mean value of 122.46 (8)°. The widening of this angle can be related to a steric hindrance between H3 of the amide group and H atom attached to C2, as the consequence of a small twist of the amide group relative to the benzene ring. The torsion angles around the C—C bond between the amide group and the benzene ring are: C1—C3—C4—O1 14.40 (13)° and C2—C3—C4—N1 14.74 (13)°.

The molecules of the title compound are connected via N—H···O, O—H···O and C—H···O hydrogen bonds (Fig. 2; Table 1) into a three-dimensional framework. All N and O atoms participate in hydrogen bonding. The IR spectrum of the title compound shows bands corresponding to the N—H and O—H stretching vibrations in the 3370 - 2480 cm^-1 region. The center of gravity of the ν_N—H and ν_O—H bands is located at ca 2960 cm^-1. The relative shifts of about 440 cm^-1 and 640 cm^-1 for N—H and O—H bands allow to classify the N—H···O and O—H···O interactions in this crystal as strong hydrogen bonds (Desiraju & Steiner, 1999).

Related literature top

For the synthesis of the title compound, see: Sułkowski et al. (2000); Shukla & Harad (2006). For bond-length data, see: Allen (2002). For hydrogen bonding, see: Desiraju & Steiner (1999).

Experimental top

The title compound was obtained according to the method described by Sułkowski et al. (2000) and Shukla & Harad (2006). Single crystal suitable for X-ray analysis was obtained from water solution. Analysis calculated: C 57.13, H 6.39, N 11.10%; found C 57.12, H 6.26, N 10.93%. IR spectra were recorded with the Perkin-Elmer Spectrum.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The H-atom radius is arbitrary. Symmetry code: (a) -x, -y + 1, -z + 1
	Fig. 2. Packing diagram for the title compound. Hydrogen bonds are shown with dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

N,N'-Bis(2-hydroxyethyl)benzene-1,4-dicarboxamide top

Crystal data top

C₁₂H₁₆N₂O₄	F(000) = 268
M_r = 252.27	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3594 reflections
a = 4.9062 (4) Å	θ = 3.0–32.8°
b = 13.6467 (10) Å	µ = 0.11 mm⁻¹
c = 8.8840 (7) Å	T = 200 K
β = 97.262 (6)°	Needle, colourless
V = 590.04 (8) Å³	0.26 × 0.22 × 0.18 mm
Z = 2

Data collection top

Oxford Diffraction KM-4-CCD Sapphire3 diffractometer	1599 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.014
Graphite monochromator	θ_max = 32.9°, θ_min = 3.0°
Detector resolution: 16.0328 pixels mm^-1	h = −7→5
ω scans	k = −19→19
5655 measured reflections	l = −13→12
2000 independent 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) = 0.097	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0542P)² + 0.0884P] where P = (F_o² + 2F_c²)/3
2000 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₆N₂O₄	V = 590.04 (8) Å³
M_r = 252.27	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.9062 (4) Å	µ = 0.11 mm⁻¹
b = 13.6467 (10) Å	T = 200 K
c = 8.8840 (7) Å	0.26 × 0.22 × 0.18 mm
β = 97.262 (6)°

Data collection top

Oxford Diffraction KM-4-CCD Sapphire3 diffractometer	1599 reflections with I > 2σ(I)
5655 measured reflections	R_int = 0.014
2000 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.097	All H-atom parameters refined
S = 1.03	Δρ_max = 0.34 e Å⁻³
2000 reflections	Δρ_min = −0.21 e Å⁻³
114 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	0.27008 (15)	0.27588 (5)	0.35222 (8)	0.03059 (17)
H8	0.422 (3)	0.3500 (13)	−0.1314 (17)	0.051 (4)*
O2	0.50462 (15)	0.40412 (5)	−0.10308 (8)	0.02923 (17)
N1	0.45385 (15)	0.39818 (5)	0.22776 (8)	0.02234 (16)
H3	0.470 (3)	0.4611 (12)	0.2100 (16)	0.043 (4)*
C1	−0.0348 (2)	0.59732 (6)	0.45869 (11)	0.02646 (19)
H1	−0.063 (3)	0.6650 (11)	0.4282 (15)	0.037 (3)*
C2	0.1105 (2)	0.53512 (7)	0.37400 (10)	0.02685 (19)
H2	0.183 (3)	0.5608 (11)	0.2851 (16)	0.044 (4)*
C3	0.14642 (16)	0.43721 (6)	0.41503 (9)	0.01995 (16)
C4	0.29698 (17)	0.36475 (6)	0.32869 (9)	0.02059 (16)
C5	0.61451 (18)	0.33030 (6)	0.14753 (10)	0.02380 (17)
H4	0.493 (2)	0.2750 (9)	0.1119 (13)	0.028 (3)*
H5	0.772 (3)	0.3050 (10)	0.2180 (15)	0.037 (3)*
C6	0.71991 (19)	0.37877 (7)	0.01299 (11)	0.02745 (19)
H6	0.851 (3)	0.3331 (10)	−0.0254 (15)	0.039 (3)*
H7	0.816 (2)	0.4390 (10)	0.0435 (14)	0.029 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0417 (4)	0.0180 (3)	0.0354 (4)	0.0064 (3)	0.0175 (3)	0.0056 (2)
O2	0.0438 (4)	0.0192 (3)	0.0259 (3)	−0.0063 (3)	0.0089 (3)	0.0005 (2)
N1	0.0275 (4)	0.0175 (3)	0.0238 (3)	0.0003 (2)	0.0099 (3)	−0.0013 (2)
C1	0.0365 (5)	0.0179 (4)	0.0276 (4)	0.0047 (3)	0.0145 (3)	0.0056 (3)
C2	0.0372 (5)	0.0203 (4)	0.0260 (4)	0.0041 (3)	0.0155 (3)	0.0052 (3)
C3	0.0229 (4)	0.0182 (3)	0.0196 (3)	0.0017 (3)	0.0057 (3)	0.0014 (3)
C4	0.0234 (3)	0.0188 (4)	0.0200 (3)	0.0025 (3)	0.0044 (3)	0.0014 (3)
C5	0.0270 (4)	0.0214 (4)	0.0243 (4)	0.0037 (3)	0.0083 (3)	−0.0013 (3)
C6	0.0288 (4)	0.0252 (4)	0.0310 (4)	−0.0020 (3)	0.0140 (3)	−0.0027 (3)

Geometric parameters (Å, º) top

O1—C4	1.2404 (10)	C3—C1ⁱ	1.3913 (12)
O2—H8	0.863 (18)	C3—C4	1.5017 (11)
N1—C4	1.3338 (11)	C5—H4	0.988 (12)
N1—C5	1.4594 (11)	C5—H5	0.992 (13)
N1—H3	0.879 (16)	C6—O2	1.4224 (12)
C1—H1	0.967 (14)	C6—C5	1.5133 (12)
C2—C1	1.3896 (12)	C6—H6	0.989 (14)
C2—C3	1.3902 (12)	C6—H7	0.970 (13)
C2—H2	0.972 (15)

C3—C2—C1	120.12 (8)	C2—C3—C4	123.58 (7)
C3—C2—H2	120.8 (9)	C1ⁱ—C3—C4	117.25 (7)
C1—C2—H2	119.0 (9)	N1—C5—C6	111.58 (7)
O2—C6—C5	112.48 (7)	N1—C5—H4	107.5 (7)
O2—C6—H7	106.7 (7)	C6—C5—H4	109.4 (7)
C5—C6—H7	110.7 (7)	N1—C5—H5	109.7 (8)
O2—C6—H6	111.1 (8)	C6—C5—H5	109.6 (8)
C5—C6—H6	107.4 (8)	H4—C5—H5	108.9 (10)
H7—C6—H6	108.4 (10)	O1—C4—N1	122.04 (8)
C6—O2—H8	106.3 (10)	O1—C4—C3	119.21 (7)
C4—N1—C5	120.29 (7)	N1—C4—C3	118.75 (7)
C4—N1—H3	122.0 (9)	C2—C1—C3ⁱ	120.73 (8)
C5—N1—H3	117.7 (9)	C2—C1—H1	119.7 (8)
C2—C3—C1ⁱ	119.16 (7)	C3ⁱ—C1—H1	119.6 (8)

C1—C2—C3—C1ⁱ	0.09 (16)	C2—C3—C4—O1	−164.62 (9)
C1—C2—C3—C4	179.10 (8)	C1ⁱ—C3—C4—O1	14.40 (13)
C4—N1—C5—C6	165.93 (8)	C2—C3—C4—N1	14.74 (13)
O2—C6—C5—N1	−66.81 (10)	C1ⁱ—C3—C4—N1	−166.23 (8)
C5—N1—C4—O1	−3.87 (13)	C3—C2—C1—C3ⁱ	−0.09 (16)
C5—N1—C4—C3	176.78 (7)

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—H3···O2ⁱⁱ	0.879 (16)	2.080 (16)	2.9333 (10)	163.3 (13)
O2—H8···O1ⁱⁱⁱ	0.863 (18)	1.872 (18)	2.7204 (9)	167.1 (15)
C2—H2···O2ⁱⁱ	0.972 (15)	2.412 (14)	3.3458 (11)	161.0 (11)
C5—H4···O1ⁱⁱⁱ	0.988 (12)	2.523 (12)	3.2738 (12)	132.6 (9)
C5—H5···O1^iv	0.992 (13)	2.612 (13)	3.5671 (12)	161.7 (11)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₄
M_r	252.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	4.9062 (4), 13.6467 (10), 8.8840 (7)
β (°)	97.262 (6)
V (Å³)	590.04 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.26 × 0.22 × 0.18

Data collection
Diffractometer	Oxford Diffraction KM-4-CCD Sapphire3 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5655, 2000, 1599
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.763

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.097, 1.03
No. of reflections	2000
No. of parameters	114
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.21

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3···O2ⁱ	0.879 (16)	2.080 (16)	2.9333 (10)	163.3 (13)
O2—H8···O1ⁱⁱ	0.863 (18)	1.872 (18)	2.7204 (9)	167.1 (15)
C2—H2···O2ⁱ	0.972 (15)	2.412 (14)	3.3458 (11)	161.0 (11)
C5—H4···O1ⁱⁱ	0.988 (12)	2.523 (12)	3.2738 (12)	132.6 (9)
C5—H5···O1ⁱⁱⁱ	0.992 (13)	2.612 (13)	3.5671 (12)	161.7 (11)

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

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. New York: Oxford University Press. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shukla, S. R. & Harad, A. M. (2006). Polym. Degrad. Stabil. 91, 1850–1854. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sułkowski, W. W., Ossowski, J., Sułkowska, A. & Bajdur, W. (2000). Abstract. 1st International Conference `Modification, Degradation and Stabilization of Polymers', p. P11, Palermo, Italy. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1277

doi:10.1107/S1600536808017467

Open

access