N,N,N′,N′-Tetra­kis(2-hydroxy­ethyl)terephthalamide

Wang, Z.-Q.; Xu, C.; Li, Y.-F.; Cen, F.-F.; Zhang, Y.-Q.

doi:10.1107/S1600536808041573

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o166

doi:10.1107/S1600536808041573

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N,N,N′,N′-Tetrakis(2-hydroxyethyl)terephthalamide

Zhi-Qiang Wang,^a ^* Chen Xu,^a Ying-Fei Li,^b Fei-Fei Cen ^b and Yu-Qing Zhang ^b

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China, and ^bChemical Engineering and Pharmaceutics School, Henan University of Science and Technology, Luoyang 471003, People's Republic of China
^*Correspondence e-mail: wzq197811@sohu.com

(Received 1 November 2008; accepted 8 December 2008; online 20 December 2008)

The molecule of the title compound, C₁₆H₂₄N₂O₆, which lies on a crystallographic inversion centre in the centre of the benzene ring, adopts an anti conformation in terms of the relative orientation of two amide carbonyl groups. One pair of the 2-hydroxyethyl groups is partially disordered with site occupancy factors of 0.811 (2) and 0.189 (2). The dihedral angle between the amide group and central benzene ring is 67.0 (2)°. Two O—H⋯O and one bifurcated O—H⋯(O,O) hydrogen bonds are present, resulting in a three-dimensional network.

Related literature

For bond-length data, see: Allen et al. (1987 ). For general background, see: Katoono et al. (2006 ); Tosin et al. (2005 ); Yin et al. (2005 ).

Experimental

Crystal data

C₁₆H₂₄N₂O₆
M_r = 340.37
Orthorhombic, P b c a
a = 10.3244 (12) Å
b = 12.5378 (14) Å
c = 12.8384 (15) Å
V = 1661.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 (2) K
0.29 × 0.24 × 0.23 mm

Data collection

Bruker SMART APEXII detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.961, T_max = 0.976
11505 measured reflections
1550 independent reflections
1273 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.126
S = 1.06
1550 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.35 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
O2—H2A⋯O3ⁱ	0.82	1.91	2.723 (9)	169
O2—H2A⋯O3′ⁱ	0.82	1.90	2.675 (10)	157
O3′—H3′⋯O2ⁱⁱ	0.82	2.31	2.675 (3)	108
O3—H3D⋯O1ⁱⁱⁱ	0.82	2.00	2.810 (2)	170
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041573/rn2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041573/rn2054Isup2.hkl

checkCIF report

Comment top

Terephthalamide derivatives are important compounds in molecular recognition and supramolecular chemistry (Yin et al., 2005; Tosin et al.,2005; Katoono et al.,2006). Although numerous tetrasubstituted terephthalamides have been investigated, only a few tetrakis(alkyl)terephthalamides are known. In order to further the study of such compounds, we report the crystal structure of the title compound.

A view of the molecular structure of the title compound is given in Fig.1. Molecules of the title compound lie across crystallographic inversion centres and adopt the anti-conformation. The bond distances and angles are normal (Allen et al., 1987). One set of the 2-hydroxyethyl groups is disordered with site occupancy factors of ca 0.811 (2) and 0.189 (2). The dihedral angle between the amide plane (C4,O1,N1) and phenyl planes (C1—C3,C1A—C3A) is 67.0 (2)°. The structural study shows the presence of four different intermolecular O—H···O hydrogen bonds (Table 1), resulting in a three-dimensional supramolecular architecture (Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For general background, see: Katoono et al. (2006); Tosin et al. (2005); Yin et al. (2005).

Experimental top

To a solution of diethanolamine (2 mmol) in dry chloroform (5 ml), at 273 K, was added dropwise a solution of terephthalyl chloride (2 mmol) in dry chloroform (25 ml). Then, the mixture stirred at room temperature for 24hr, removal of solvent resulted in a yellow powder that was recrystallized from methanol-DMF solution at room temperature to give the desired product as colourless crystals suitable for single-crystal X-ray diffraction.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 30% probability level (suffix A denotes the symmetry code: -x + 2, -y, -z + 1).
	Fig. 2. Partial view of the crystal packing showing the intermolecular O—H···O hydrogen bonds.

N,N,N',N'-Tetrakis(2-hydroxyethyl)terephthalamide top

Crystal data top

C₁₆H₂₄N₂O₆	D_x = 1.360 Mg m⁻³
M_r = 340.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3593 reflections
a = 10.3244 (12) Å	θ = 3.0–23.6°
b = 12.5378 (14) Å	µ = 0.10 mm⁻¹
c = 12.8384 (15) Å	T = 296 K
V = 1661.9 (3) Å³	Block, colourless
Z = 4	0.29 × 0.24 × 0.23 mm
F(000) = 728

Data collection top

Bruker SMART APEXII detector diffractometer	1550 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.961, T_max = 0.976	k = −15→15
11505 measured reflections	l = −15→15

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) = 0.126	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.061P)² + 0.6392P] where P = (F_o² + 2F_c²)/3
1550 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₆H₂₄N₂O₆	V = 1661.9 (3) Å³
M_r = 340.37	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 10.3244 (12) Å	µ = 0.10 mm⁻¹
b = 12.5378 (14) Å	T = 296 K
c = 12.8384 (15) Å	0.29 × 0.24 × 0.23 mm

Data collection top

Bruker SMART APEXII detector diffractometer	1550 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1273 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.976	R_int = 0.022
11505 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.06	Δρ_max = 0.35 e Å⁻³
1550 reflections	Δρ_min = −0.21 e Å⁻³
111 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	Occ. (<1)
C7	0.78238 (19)	0.31459 (17)	0.30476 (16)	0.0460 (6)	0.811 (2)
H7A	0.8162	0.3857	0.3168	0.055*	0.811 (2)
H7B	0.8130	0.2906	0.2373	0.055*	0.811 (2)
C8	0.63782 (13)	0.31829 (14)	0.30437 (14)	0.0498 (6)	0.811 (2)
H8A	0.6033	0.2481	0.2887	0.060*	0.811 (2)
H8B	0.6064	0.3396	0.3725	0.060*	0.811 (2)
O3	0.59529 (19)	0.39348 (12)	0.22709 (12)	0.0569 (6)	0.811 (2)
H3D	0.6203	0.4534	0.2429	0.085*	0.811 (2)
C7'	0.70527 (19)	0.28471 (18)	0.34485 (17)	0.0460 (6)	0.189 (2)
H7'1	0.6561	0.3216	0.3982	0.055*	0.189 (2)
H7'2	0.6523	0.2288	0.3147	0.055*	0.189 (2)
C8'	0.75511 (17)	0.36199 (17)	0.26151 (16)	0.0498 (6)	0.189 (2)
H8'1	0.8070	0.4170	0.2944	0.060*	0.189 (2)
H8'2	0.8102	0.3236	0.2131	0.060*	0.189 (2)
O3'	0.6539 (2)	0.40926 (16)	0.20721 (15)	0.0569 (6)	0.189 (2)
H3'	0.5952	0.3659	0.1996	0.085*	0.189 (2)
C1	0.93464 (15)	0.07120 (12)	0.43518 (12)	0.0362 (4)
C2	1.06224 (16)	0.04283 (12)	0.41398 (13)	0.0392 (4)
H2	1.1041	0.0714	0.3562	0.047*
C3	1.12701 (16)	−0.02751 (13)	0.47837 (14)	0.0405 (4)
H3	1.2124	−0.0458	0.4638	0.049*
C4	0.86624 (17)	0.14222 (13)	0.35884 (14)	0.0436 (4)
C5	0.84524 (17)	0.28318 (13)	0.49384 (14)	0.0440 (4)
H5A	0.8715	0.2257	0.5398	0.053*
H5B	0.7615	0.3087	0.5175	0.053*
C6	0.94175 (18)	0.37226 (15)	0.50233 (16)	0.0492 (5)
H6A	0.9164	0.4296	0.4559	0.059*
H6B	0.9410	0.3999	0.5729	0.059*
N1	0.83155 (14)	0.24090 (12)	0.38745 (12)	0.0496 (4)
O1	0.84678 (17)	0.10814 (11)	0.26939 (11)	0.0669 (5)
O2	1.06824 (13)	0.33898 (13)	0.47707 (12)	0.0645 (5)
H2A	1.0808	0.3474	0.4145	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0484 (13)	0.0439 (12)	0.0455 (12)	0.0069 (9)	−0.0011 (9)	0.0099 (9)
C8	0.0524 (13)	0.0459 (12)	0.0510 (13)	0.0052 (10)	−0.0096 (10)	0.0017 (10)
O3	0.0677 (14)	0.0500 (9)	0.0530 (11)	0.0135 (9)	−0.0240 (9)	−0.0022 (7)
C7'	0.0484 (13)	0.0439 (12)	0.0455 (12)	0.0069 (9)	−0.0011 (9)	0.0099 (9)
C8'	0.0524 (13)	0.0459 (12)	0.0510 (13)	0.0052 (10)	−0.0096 (10)	0.0017 (10)
O3'	0.0677 (14)	0.0500 (9)	0.0530 (11)	0.0135 (9)	−0.0240 (9)	−0.0022 (7)
C1	0.0407 (9)	0.0283 (8)	0.0397 (9)	0.0003 (6)	−0.0054 (7)	−0.0037 (7)
C2	0.0428 (9)	0.0343 (8)	0.0405 (9)	−0.0014 (7)	0.0026 (7)	0.0014 (7)
C3	0.0340 (8)	0.0362 (8)	0.0514 (10)	0.0022 (7)	0.0006 (7)	−0.0013 (7)
C4	0.0482 (10)	0.0382 (9)	0.0445 (9)	0.0042 (7)	−0.0087 (8)	−0.0018 (7)
C5	0.0449 (9)	0.0377 (9)	0.0494 (10)	0.0065 (7)	0.0000 (7)	−0.0032 (8)
C6	0.0548 (11)	0.0423 (10)	0.0505 (10)	−0.0013 (8)	0.0010 (9)	−0.0028 (8)
N1	0.0605 (10)	0.0382 (8)	0.0500 (9)	0.0135 (7)	−0.0178 (7)	−0.0031 (7)
O1	0.1004 (12)	0.0534 (8)	0.0468 (8)	0.0175 (7)	−0.0234 (8)	−0.0089 (6)
O2	0.0476 (8)	0.0816 (11)	0.0641 (9)	−0.0001 (7)	0.0030 (7)	0.0111 (8)

Geometric parameters (Å, º) top

C7—C8	1.4933 (14)	C1—C3ⁱ	1.392 (2)
C7—N1	1.496 (2)	C1—C4	1.501 (2)
C7—H7A	0.9700	C2—C3	1.382 (2)
C7—H7B	0.9700	C2—H2	0.9300
C8—O3	1.4372 (14)	C3—C1ⁱ	1.392 (2)
C8—H8A	0.9700	C3—H3	0.9300
C8—H8B	0.9700	C4—O1	1.242 (2)
O3—H3D	0.8200	C4—N1	1.339 (2)
C7'—N1	1.517 (2)	C5—N1	1.472 (2)
C7'—C8'	1.5324 (15)	C5—C6	1.501 (3)
C7'—H7'1	0.9700	C5—H5A	0.9700
C7'—H7'2	0.9700	C5—H5B	0.9700
C8'—O3'	1.3890 (13)	C6—O2	1.409 (2)
C8'—H8'1	0.9700	C6—H6A	0.9700
C8'—H8'2	0.9700	C6—H6B	0.9700
O3'—H3'	0.8200	O2—H2A	0.8200
C1—C2	1.391 (2)

C8—C7—N1	111.14 (14)	C3—C2—C1	120.30 (16)
C8—C7—H7A	109.4	C3—C2—H2	119.8
N1—C7—H7A	109.4	C1—C2—H2	119.8
C8—C7—H7B	109.4	C2—C3—C1ⁱ	120.47 (15)
N1—C7—H7B	109.4	C2—C3—H3	119.8
H7A—C7—H7B	108.0	C1ⁱ—C3—H3	119.8
O3—C8—C7	109.1	O1—C4—N1	121.89 (16)
O3—C8—H8A	109.9	O1—C4—C1	118.42 (15)
C7—C8—H8A	109.9	N1—C4—C1	119.66 (15)
O3—C8—H8B	109.9	N1—C5—C6	113.53 (15)
C7—C8—H8B	109.9	N1—C5—H5A	108.9
H8A—C8—H8B	108.3	C6—C5—H5A	108.9
N1—C7'—C8'	101.08 (14)	N1—C5—H5B	108.9
N1—C7'—H7'1	111.6	C6—C5—H5B	108.9
C8'—C7'—H7'1	111.6	H5A—C5—H5B	107.7
N1—C7'—H7'2	111.6	O2—C6—C5	112.23 (15)
C8'—C7'—H7'2	111.6	O2—C6—H6A	109.2
H7'1—C7'—H7'2	109.4	C5—C6—H6A	109.2
O3'—C8'—C7'	111.6	O2—C6—H6B	109.2
O3'—C8'—H8'1	109.3	C5—C6—H6B	109.2
C7'—C8'—H8'1	109.3	H6A—C6—H6B	107.9
O3'—C8'—H8'2	109.3	C4—N1—C5	124.16 (14)
C7'—C8'—H8'2	109.3	C4—N1—C7	117.81 (15)
H8'1—C8'—H8'2	108.0	C5—N1—C7	117.94 (14)
C8'—O3'—H3'	109.5	C4—N1—C7'	117.74 (16)
C2—C1—C3ⁱ	119.23 (15)	C5—N1—C7'	106.66 (15)
C2—C1—C4	118.00 (15)	C7—N1—C7'	39.54 (8)
C3ⁱ—C1—C4	122.62 (15)	C6—O2—H2A	109.5

N1—C7—C8—O3	177.43 (15)	C1—C4—N1—C7	170.75 (15)
N1—C7'—C8'—O3'	177.19 (14)	O1—C4—N1—C7'	37.8 (3)
C3ⁱ—C1—C2—C3	−0.3 (3)	C1—C4—N1—C7'	−144.29 (16)
C4—C1—C2—C3	−176.06 (15)	C6—C5—N1—C4	113.8 (2)
C1—C2—C3—C1ⁱ	0.3 (3)	C6—C5—N1—C7	−62.8 (2)
C2—C1—C4—O1	64.1 (2)	C6—C5—N1—C7'	−104.03 (17)
C3ⁱ—C1—C4—O1	−111.5 (2)	C8—C7—N1—C4	98.8 (2)
C2—C1—C4—N1	−113.88 (19)	C8—C7—N1—C5	−84.3 (2)
C3ⁱ—C1—C4—N1	70.5 (2)	C8—C7—N1—C7'	−1.98 (10)
N1—C5—C6—O2	−63.2 (2)	C8'—C7'—N1—C4	−104.2 (2)
O1—C4—N1—C5	176.24 (18)	C8'—C7'—N1—C5	110.73 (19)
C1—C4—N1—C5	−5.8 (3)	C8'—C7'—N1—C7	−3.21 (8)
O1—C4—N1—C7	−7.2 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3ⁱⁱ	0.82	1.91	2.723 (9)	169
O2—H2A···O3′ⁱⁱ	0.82	1.90	2.675 (10)	157
O3′—H3′···O2ⁱⁱⁱ	0.82	2.31	2.675 (3)	108
O3—H3D···O1^iv	0.82	2.00	2.810 (2)	170

Symmetry codes: (ii) x+1/2, y, −z+1/2; (iii) x−1/2, y, −z+1/2; (iv) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₄N₂O₆
M_r	340.37
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	10.3244 (12), 12.5378 (14), 12.8384 (15)
V (Å³)	1661.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.29 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART APEXII detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	11505, 1550, 1273
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.126, 1.06
No. of reflections	1550
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3ⁱ	0.82	1.91	2.723 (9)	169.0
O2—H2A···O3'ⁱ	0.82	1.90	2.675 (10)	157.0
O3'—H3'···O2ⁱⁱ	0.82	2.31	2.675 (3)	107.7
O3—H3D···O1ⁱⁱⁱ	0.82	2.00	2.810 (2)	170.0

Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, y, −z+1/2; (iii) −x+3/2, y+1/2, z.

Acknowledgements

This work was supported by the Doctoral Foundation of Luoyang Normal University.

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