2,2′-Dihydroxy-N,N′-(ethane-1,2-di­yl)di­benzamide

Costa, D.P. da; Nobre, S.M.; Lisboa, B.G.; Vicenti, J.R. de M.; Back, D.F.

doi:10.1107/S1600536812051963

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o201

doi:10.1107/S1600536812051963

Open

access

2,2′-Dihydroxy-N,N′-(ethane-1,2-diyl)dibenzamide

Daniel Pereira da Costa,^a Sabrina Madruga Nobre,^a ^* Bruna Gonçalves Lisboa,^a Juliano Rosa de Menezes Vicenti ^a and Davi Fernando Back ^b

^aEscola de Quimica e Alimentos, Universidade Federal do Rio Grande, Av. Italia, km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil, and ^bDepartamento de Quimica, Universidade Federal de Santa Maria, Av. Roraima Campus, 97105-900 Santa Maria-RS, Brazil
^*Correspondence e-mail: sabrinanobre@furg.br

(Received 20 December 2012; accepted 27 December 2012; online 9 January 2013)

The asymmetric unit of the title compound, C₁₆H₁₆N₂O₄, contains one half-molecule, the whole molecule being generated by an inversion center located at the mid-point of the C—C bond of the central ethane group. An intramolecular O—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, molecules are connected via N—H⋯O hydrogen bonds, generating infinite chains along [1-10].

Related literature

For the synthesis of bisamides, see: Apurba et al. (2002 ); Fry et al. (2010 ). For similar bisamide crystal structures, see: Booysen et al. (2009 ). For applications of bisamides as catalysts, see: Maurya et al. (2003 ); Liu et al. (2011 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₄
M_r = 300.31
Triclinic, $[P \overline 1]$
a = 4.6311 (3) Å
b = 5.0435 (3) Å
c = 15.2957 (9) Å
α = 89.091 (4)°
β = 83.315 (4)°
γ = 85.956 (4)°
V = 353.94 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.34 × 0.24 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: gaussian (SADABS; Bruker, 2009 ) T_min = 0.966, T_max = 0.989
9142 measured reflections
1535 independent reflections
924 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.143
S = 1.01
1535 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	1.76	2.495 (2)	148
N—H0⋯O1ⁱ	0.86	2.21	2.993 (2)	151
Symmetry code: (i) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812051963/lr2096sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812051963/lr2096Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812051963/lr2096Isup3.cml

checkCIF report

Comment top

Nitrogenated compound amines, imines and amides are part of a broad class of molecules having a pharmacological and technological profile (Fry et al. 2010). Bisamides can be synthesized from a reaction between a diamine and an acylhalide under reflux (Apurba et al. 2002 ; Fry et al. 2010). Some synthesized bisamides have had their crystal structure determined (Booysen et al. 2009). However, others have been synthesized and applied to several reactions, such as the hydroformylation of phenol (Maurya et al. 2003) and due to the simplicity of the synthesis of these compounds, they have being applied to coupling reactions, such as the Suzuki reaction (Liu et al. 2011). The asymmetric unit is formed by one half of the molecule and the whole molecule is generated through a crystallographic center of symmetry placed in the mid-point of the C-C bond of the ethane bridging moiety (Fig. 1). Intramolecular and intermolecular classical hydrogen bond interactions are observed in the solid state. Each molecule participates in intermolecular hydrogen bond interactions with two other neighboring molecules through Nⁱⁱ–H0ⁱⁱ···O1 with a distance of 2.210 Å (symmetry code: (ii) -1 + x, 1 + y, z). The intramolecular hydrogen bonding systems forms six membered rings, showing a shorter distance of 1.763 Å (O2···H1–O1). These hydrogen bonding may contribute to the stabilization of the crystal structure (Fig. 2).

Related literature top

For the synthesis of bisamides, see: Apurba et al. (2002); Fry et al. (2010). For similar bisamide crystal structures, see: Booysen et al. (2009). For applications of bisamides as catalysts, see: Maurya et al. (2003); Liu et al. (2011).

Experimental top

Ethylenediamine (0.1 mol, 6.6 ml) was added to a solution containing methyl salicylate (0.2 mol, 25.7 ml). The mixture was refluxed for 7 h. The reaction product was washed with ethyl acetate (3 times in 30 ml) and dried over CaCl₂. After recrystallization from hexane, a yellow solid was obtained (23.1 g, 77%).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular projection showing the asymmetric unit represented in dark colors. Ellipsoid probability: 50%. Symmetry codes: (i) 2–x, 1–y, 2–z
	Fig. 2. Packing diagram view showing the intramolecular e intermolecular hydrogen bond interactions. Some hydrogen atoms were omitted for clarity. (ii) -1 + x, 1 + y, z

2,2'-Dihydroxy-N,N'-(ethane-1,2-diyl)dibenzamide top

Crystal data top

C₁₆H₁₆N₂O₄	Z = 1
M_r = 300.31	F(000) = 158
Triclinic, P1	D_x = 1.409 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.6311 (3) Å	Cell parameters from 1575 reflections
b = 5.0435 (3) Å	θ = 2.7–25.8°
c = 15.2957 (9) Å	µ = 0.10 mm⁻¹
α = 89.091 (4)°	T = 296 K
β = 83.315 (4)°	Block, colourless
γ = 85.956 (4)°	0.34 × 0.24 × 0.11 mm
V = 353.94 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	1535 independent reflections
Radiation source: fine-focus sealed tube	924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 27.1°, θ_min = 2.7°
Absorption correction: gaussian (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.966, T_max = 0.989	k = −6→6
9142 measured reflections	l = −19→19

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0644P)² + 0.0596P] where P = (F_o² + 2F_c²)/3
1535 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₄	γ = 85.956 (4)°
M_r = 300.31	V = 353.94 (4) Å³
Triclinic, P1	Z = 1
a = 4.6311 (3) Å	Mo Kα radiation
b = 5.0435 (3) Å	µ = 0.10 mm⁻¹
c = 15.2957 (9) Å	T = 296 K
α = 89.091 (4)°	0.34 × 0.24 × 0.11 mm
β = 83.315 (4)°

Data collection top

Bruker APEXII CCD diffractometer	1535 independent reflections
Absorption correction: gaussian (SADABS; Bruker, 2009)	924 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.989	R_int = 0.033
9142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.01	Δρ_max = 0.13 e Å⁻³
1535 reflections	Δρ_min = −0.16 e Å⁻³
100 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.4041 (3)	1.1108 (3)	0.79344 (10)	0.0718 (5)
H1	0.4677	1.0900	0.8411	0.108*
O2	0.7318 (3)	0.9317 (3)	0.90207 (9)	0.0629 (5)
N	1.0113 (3)	0.5534 (3)	0.87856 (10)	0.0507 (5)
H0	1.0709	0.4248	0.8433	0.061*
C1	0.7459 (4)	0.7361 (3)	0.76153 (11)	0.0426 (5)
C2	0.5357 (4)	0.9263 (4)	0.73646 (12)	0.0496 (5)
C3	0.4584 (5)	0.9234 (5)	0.65190 (15)	0.0676 (6)
H3	0.3184	1.0495	0.6352	0.081*
C4	0.5845 (5)	0.7384 (4)	0.59253 (14)	0.0649 (6)
H4	0.5312	0.7405	0.5357	0.078*
C5	0.7895 (5)	0.5493 (5)	0.61620 (14)	0.0655 (6)
H5	0.8742	0.4220	0.5760	0.079*
C6	0.8674 (5)	0.5507 (4)	0.69979 (13)	0.0589 (6)
H6	1.0068	0.4226	0.7156	0.071*
C7	0.8293 (4)	0.7466 (4)	0.85175 (12)	0.0448 (5)
C8	1.1112 (4)	0.5513 (4)	0.96491 (12)	0.0523 (5)
H8A	1.1517	0.7304	0.9796	0.063*
H8B	1.2913	0.4402	0.9636	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0882 (11)	0.0606 (9)	0.0622 (9)	0.0348 (8)	−0.0120 (8)	−0.0122 (7)
O2	0.0780 (10)	0.0543 (9)	0.0545 (9)	0.0202 (7)	−0.0125 (7)	−0.0214 (7)
N	0.0591 (10)	0.0484 (10)	0.0439 (9)	0.0123 (8)	−0.0115 (7)	−0.0116 (7)
C1	0.0458 (10)	0.0388 (10)	0.0426 (10)	0.0022 (8)	−0.0050 (8)	−0.0043 (8)
C2	0.0569 (11)	0.0402 (10)	0.0501 (11)	0.0053 (9)	−0.0049 (9)	−0.0011 (9)
C3	0.0806 (15)	0.0620 (14)	0.0601 (13)	0.0147 (12)	−0.0198 (12)	0.0036 (11)
C4	0.0828 (16)	0.0679 (15)	0.0459 (12)	−0.0029 (12)	−0.0165 (11)	−0.0007 (11)
C5	0.0820 (15)	0.0642 (14)	0.0490 (12)	0.0113 (12)	−0.0094 (11)	−0.0158 (10)
C6	0.0696 (13)	0.0567 (13)	0.0488 (12)	0.0176 (10)	−0.0111 (10)	−0.0120 (10)
C7	0.0458 (10)	0.0420 (10)	0.0456 (10)	0.0040 (8)	−0.0041 (8)	−0.0085 (8)
C8	0.0540 (11)	0.0563 (12)	0.0477 (11)	0.0058 (9)	−0.0154 (8)	−0.0091 (9)

Geometric parameters (Å, º) top

O1—C2	1.349 (2)	C3—C4	1.365 (3)
O1—H1	0.8206	C3—H3	0.9300
O2—C7	1.245 (2)	C4—C5	1.372 (3)
N—C7	1.334 (2)	C4—H4	0.9300
N—C8	1.449 (2)	C5—C6	1.369 (3)
N—H0	0.8600	C5—H5	0.9300
C1—C6	1.383 (2)	C6—H6	0.9300
C1—C2	1.400 (3)	C8—C8ⁱ	1.511 (4)
C1—C7	1.478 (2)	C8—H8A	0.9700
C2—C3	1.382 (3)	C8—H8B	0.9700

C2—O1—H1	109.5	C6—C5—C4	119.07 (19)
C7—N—C8	122.58 (15)	C6—C5—H5	120.5
C7—N—H0	118.6	C4—C5—H5	120.5
C8—N—H0	118.8	C5—C6—C1	122.21 (18)
C6—C1—C2	117.95 (17)	C5—C6—H6	118.9
C6—C1—C7	123.62 (16)	C1—C6—H6	118.9
C2—C1—C7	118.42 (15)	O2—C7—N	120.36 (17)
O1—C2—C3	119.21 (17)	O2—C7—C1	120.87 (16)
O1—C2—C1	121.37 (17)	N—C7—C1	118.78 (15)
C3—C2—C1	119.42 (17)	N—C8—C8ⁱ	112.0 (2)
C4—C3—C2	120.98 (19)	N—C8—H8A	109.2
C4—C3—H3	119.5	C8ⁱ—C8—H8A	109.2
C2—C3—H3	119.5	N—C8—H8B	109.2
C3—C4—C5	120.4 (2)	C8ⁱ—C8—H8B	109.2
C3—C4—H4	119.8	H8A—C8—H8B	107.9
C5—C4—H4	119.8

C6—C1—C2—O1	178.94 (18)	C2—C1—C6—C5	0.3 (3)
C7—C1—C2—O1	−2.0 (3)	C7—C1—C6—C5	−178.7 (2)
C6—C1—C2—C3	−0.3 (3)	C8—N—C7—O2	−1.8 (3)
C7—C1—C2—C3	178.77 (19)	C8—N—C7—C1	178.24 (17)
O1—C2—C3—C4	−179.4 (2)	C6—C1—C7—O2	173.61 (19)
C1—C2—C3—C4	−0.2 (4)	C2—C1—C7—O2	−5.4 (3)
C2—C3—C4—C5	0.6 (4)	C6—C1—C7—N	−6.5 (3)
C3—C4—C5—C6	−0.6 (4)	C2—C1—C7—N	174.55 (17)
C4—C5—C6—C1	0.2 (4)	C7—N—C8—C8ⁱ	80.7 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.76	2.495 (2)	148
N—H0···O1ⁱⁱ	0.86	2.21	2.993 (2)	151

Symmetry code: (ii) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₄
M_r	300.31
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	4.6311 (3), 5.0435 (3), 15.2957 (9)
α, β, γ (°)	89.091 (4), 83.315 (4), 85.956 (4)
V (Å³)	353.94 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.34 × 0.24 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Gaussian (SADABS; Bruker, 2009)
T_min, T_max	0.966, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	9142, 1535, 924
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.143, 1.01
No. of reflections	1535
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.76	2.495 (2)	148
N—H0···O1ⁱ	0.86	2.21	2.993 (2)	151

Symmetry code: (i) x+1, y−1, z.

Acknowledgements

The authors gratefully acknowledge Professor Manfredo Hörner, Department of Chemistry, Universidade Federal de Santa Maria, Brazil, for his support and help with the X-ray measurements. They also thank PRONEX FAPERGS/CNPq 10/0009–2 and PRONEM FAPERGS/CNPq 11/2026–4 for funding this study.

References

Apurba, K., Patra, A. K., Olmstead, M. M. & Mascharak, P. K. (2002). Inorg. Chem. 41, 5403–5409. Web of Science PubMed Google Scholar
Booysen, I., Gerber, T. I. A., Hosten, E. & Mayer, P. (2009). Acta Cryst. E65, o850. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fry, N. L., Rose, M. J., Rogow, D. L., Nyitray, C., Kaur, M. & Mascharak, P. K. (2010). Inorg. Chem. 49, 1487–1495. Web of Science CSD CrossRef CAS PubMed Google Scholar
Liu, H. Y., Wang, K., Fu, H. Y., Yuan, M. L. & Chen, H. (2011). Chin. Chem. Lett. 22, 738–740. Web of Science CrossRef CAS Google Scholar
Maurya, M. R., Titinchi, S. J. J. & Chand, S. (2003). Catal. Lett. 89, 219–227. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar