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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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%).

Refinement

H atoms attached to aromatic C atoms were positioned with idealized geometry and were refined isotropic with U_eq(H) set to 1.2 times of the U_eq(C) using a riding model with C–H = 0.93 Å. H atoms attached to N atoms and to the ethylene fragment were located in difference Fourier maps. Their positional and isotropic displacement parameters were refined.

Figures

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

Crystal data

C16H16N2O4	Z = 1
Mr = 300.31	F(000) = 158
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.0644P)2 + 0.0596P] where P = (Fo2 + 2Fc2)/3
1535 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.13 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.