1,2-Ethyl­enediaminium bis­(2-benzamido­benzoate)

Ziyaev, M.; Ashurov, J.; Talipov, S.; Ibragimov, B.

doi:10.1107/S1600536813021028

organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1388

doi:10.1107/S1600536813021028

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1,2-Ethylenediaminium bis(2-benzamidobenzoate)

Mavlonbek Ziyaev,^a ^* Jamshid Ashurov,^a Samat Talipov ^a and Bakhtiyar Ibragimov ^a

^aInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek Str. 83, Tashkent 100125, Uzbekistan
^*Correspondence e-mail: kimyogar8221@mail.ru

(Received 17 June 2013; accepted 28 July 2013; online 7 August 2013)

In the title salt, C₂H₁₀N₂²⁺·2C₁₄H₁₀NO₃⁻, the ethylenediaminium dication lies on an inversion centre. In the anion, the benzene rings make a dihedral angle of 33.87 (9)° and intramolecular N—H⋯O and C—H⋯O hydrogen bonds occur. All the amino H atoms are involved in N—H⋯O hydrogen bonds. These hydrogen bonds link the ionic units into a three-dimensional network. In addition, the crystal structure also features weak C—H⋯O interactions.

Related literature

For the crystal structure of 1,2-ethylenediammonium salts of aromatic acids, see: Shen-Tu et al. (2008 ); Zhao & Feng (2011 ). For the crystal structure of the 2-benzamidobenzoyl acid Cu^II coordination compound, see: Kaizer et al. (2006 ).

Experimental

Crystal data

0.5C₂H₁₀N₂²⁺·C₁₄H₁₀NO₃⁻
M_r = 271.29
Monoclinic, P 2₁ /n
a = 5.314 (1) Å
b = 13.745 (2) Å
c = 18.580 (4) Å
β = 93.66 (2)°
V = 1354.3 (4) Å³
Z = 4
Cu Kα radiation
μ = 0.77 mm⁻¹
T = 293 K
0.6 × 0.3 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.699, T_max = 1.000
5702 measured reflections
2772 independent reflections
1851 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.117
S = 0.95
2772 reflections
197 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.90 (2)	1.81 (2)	2.608 (2)	146.8 (19)
N1s—H1A⋯O1	0.94 (2)	1.89 (2)	2.807 (2)	165 (2)
N1s—H1B⋯O3ⁱ	0.98 (2)	1.76 (2)	2.729 (2)	170 (2)
N1s—H1C⋯O2ⁱⁱ	0.94 (2)	1.84 (2)	2.753 (2)	163 (2)
C2s—H2B⋯O3ⁱⁱⁱ	0.97	2.59	3.315 (2)	131
C6—H6⋯O3ⁱⁱⁱ	0.93	2.50	3.319 (2)	147
C9—H9⋯O1	0.93	2.25	2.863 (2)	123
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, GLOBAL. DOI: 10.1107/S1600536813021028/zq2204sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021028/zq2204Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021028/zq2204Isup3.cml

checkCIF report

Comment top

The asymmetric unit is composed of one 2-benzamidobenzoate anion and one-half of the ethylenediaminium cation (Fig. 1). In the 2-benzamidobenzoate anion the carboxylate group is slightly rotated with respect to the benzene ring, the dihedral angle between the mean planes is 6.1 (1)°, while the peptide bond exhibits an angle of 6.1 (8)° relative to the benzene ring. The angle between the peptide bond and the second benzene ring is 29.6 (7)°. An intramolecular N—H···O hydrogen bond is observed between the amino group and one O atom of the carboxylate (Table 1). Both amine N atoms of the ethylenediamine are protonated and all nitrogen H atoms are involved in N—H···O hydrogen bonds (Table 1, Fig. 2). In the crystal structure, anions are bridged by diammonium N–H(b) and N–H(c) bonds via the carboxylate O atoms forming centrosymmetrical H-bonded strands along the a axis. Other intermolecular N—H···O hydrogen bonds between the diammonium N–H(a) bonds and the carbonyl O atoms link these strands into sheets parallel to (011) and (0–11) planes forming a three-dimensional network. In addition, C—H···O weak interactions further stabilize the crystal structure. Some related crystal structures of interest were previously reported by Shen-Tu et al. (2008), Zhao and Feng (2011) and Kaizer et al. (2006).

Related literature top

For the crystal structure of 1,2-ethylenediammonium salts of aromatic acids, see: Shen-Tu et al. (2008); Zhao & Feng (2011). For the crystal structure of the 2-benzamidobenzoyl acid Cu^II coordination compound, see: Kaizer et al. (2006).

Experimental top

A 1:2 mixture of 1,2-ethylenediamine and 2-benzamidobenzoic acid were dissolved in ethanol. Colourless prismatic crystals suitable for a X-ray analysis were obtained after 5 days.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View of the crystal structure along the a axis showing N—H···O hydrogen bonds (dashed lines).

1,2-Ethylenediaminium bis(2-benzamidobenzoate) top

Crystal data top

0.5C₂H₁₀N₂²⁺·C₁₄H₁₀NO₃⁻	F(000) = 572
M_r = 271.29	D_x = 1.331 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 753 reflections
a = 5.314 (1) Å	θ = 4.0–75.3°
b = 13.745 (2) Å	µ = 0.77 mm⁻¹
c = 18.580 (4) Å	T = 293 K
β = 93.66 (2)°	Prism, colourless
V = 1354.3 (4) Å³	0.6 × 0.3 × 0.2 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	2772 independent reflections
Radiation source: fine-focus sealed tube	1851 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.2576 pixels mm^-1	θ_max = 75.9°, θ_min = 4.0°
ω scans	h = −5→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −16→16
T_min = 0.699, T_max = 1.000	l = −23→23
5702 measured 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
2772 reflections	(Δ/σ)_max < 0.001
197 parameters	Δρ_max = 0.15 e Å⁻³
3 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

0.5C₂H₁₀N₂²⁺·C₁₄H₁₀NO₃⁻	V = 1354.3 (4) Å³
M_r = 271.29	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 5.314 (1) Å	µ = 0.77 mm⁻¹
b = 13.745 (2) Å	T = 293 K
c = 18.580 (4) Å	0.6 × 0.3 × 0.2 mm
β = 93.66 (2)°

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	2772 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1851 reflections with I > 2σ(I)
T_min = 0.699, T_max = 1.000	R_int = 0.029
5702 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.15 e Å⁻³
2772 reflections	Δρ_min = −0.17 e Å⁻³
197 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	0.9888 (3)	0.12659 (9)	0.12307 (7)	0.0596 (4)
O2	1.0308 (2)	0.35350 (9)	0.32469 (7)	0.0589 (4)
O3	1.3389 (2)	0.35553 (9)	0.41015 (6)	0.0563 (4)
N1	1.0384 (3)	0.22290 (11)	0.22300 (7)	0.0441 (3)
H1	0.990 (4)	0.2773 (15)	0.2457 (11)	0.069 (6)*
C1	0.7412 (3)	0.27034 (13)	0.12662 (9)	0.0441 (4)
C2	0.5906 (3)	0.32616 (14)	0.16836 (10)	0.0528 (5)
H2	0.6089	0.3221	0.2184	0.063*
C3	0.4114 (4)	0.38855 (16)	0.13553 (13)	0.0678 (6)
H3	0.3084	0.4256	0.1635	0.081*
C4	0.3873 (4)	0.39519 (17)	0.06148 (14)	0.0761 (7)
H4	0.2667	0.4364	0.0394	0.091*
C5	0.5398 (5)	0.34150 (18)	0.02018 (12)	0.0758 (7)
H5	0.5256	0.3476	−0.0298	0.091*
C6	0.7144 (4)	0.27842 (15)	0.05216 (10)	0.0592 (5)
H6	0.8148	0.2410	0.0237	0.071*
C7	0.9329 (3)	0.19958 (13)	0.15740 (8)	0.0440 (4)
C8	1.2370 (3)	0.17703 (12)	0.26353 (8)	0.0407 (4)
C9	1.3484 (4)	0.09159 (13)	0.24163 (9)	0.0517 (4)
H9	1.2873	0.0611	0.1994	0.062*
C10	1.5489 (4)	0.05158 (14)	0.28199 (10)	0.0582 (5)
H10	1.6229	−0.0054	0.2665	0.070*
C11	1.6410 (4)	0.09508 (15)	0.34524 (11)	0.0609 (5)
H11	1.7753	0.0676	0.3726	0.073*
C12	1.5309 (3)	0.17992 (14)	0.36727 (9)	0.0528 (5)
H12	1.5931	0.2092	0.4099	0.063*
C13	1.3301 (3)	0.22301 (12)	0.32778 (8)	0.0405 (4)
C14	1.2281 (3)	0.31706 (13)	0.35585 (8)	0.0431 (4)
N1S	0.7225 (3)	−0.04084 (12)	0.07687 (8)	0.0487 (4)
H1A	0.784 (4)	0.0205 (12)	0.0916 (10)	0.074 (7)*
H1B	0.869 (4)	−0.0844 (15)	0.0810 (12)	0.086 (7)*
H1C	0.612 (4)	−0.0677 (16)	0.1087 (10)	0.081 (7)*
C2S	0.6042 (3)	−0.03697 (13)	0.00242 (8)	0.0455 (4)
H2A	0.5369	−0.1005	−0.0110	0.055*
H2B	0.7303	−0.0199	−0.0309	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0732 (8)	0.0542 (8)	0.0492 (7)	0.0034 (7)	−0.0132 (6)	−0.0188 (6)
O2	0.0714 (9)	0.0551 (8)	0.0482 (7)	0.0153 (7)	−0.0127 (6)	−0.0139 (6)
O3	0.0657 (8)	0.0587 (8)	0.0432 (6)	−0.0028 (7)	−0.0074 (5)	−0.0163 (6)
N1	0.0558 (8)	0.0405 (8)	0.0349 (7)	0.0005 (7)	−0.0062 (6)	−0.0052 (6)
C1	0.0458 (9)	0.0437 (9)	0.0417 (8)	−0.0107 (7)	−0.0059 (7)	−0.0015 (7)
C2	0.0517 (10)	0.0550 (11)	0.0515 (10)	−0.0089 (9)	0.0014 (8)	−0.0004 (9)
C3	0.0528 (11)	0.0610 (13)	0.0891 (16)	0.0023 (10)	0.0010 (10)	−0.0037 (12)
C4	0.0657 (13)	0.0706 (15)	0.0881 (17)	0.0003 (12)	−0.0257 (12)	0.0134 (13)
C5	0.0872 (16)	0.0810 (16)	0.0556 (12)	0.0008 (14)	−0.0229 (11)	0.0081 (11)
C6	0.0674 (12)	0.0656 (12)	0.0425 (9)	−0.0035 (10)	−0.0127 (8)	−0.0046 (9)
C7	0.0515 (9)	0.0440 (9)	0.0359 (8)	−0.0081 (8)	−0.0017 (7)	−0.0048 (7)
C8	0.0482 (9)	0.0382 (8)	0.0352 (8)	−0.0022 (7)	−0.0009 (6)	0.0007 (7)
C9	0.0648 (11)	0.0439 (9)	0.0454 (9)	0.0003 (9)	−0.0052 (8)	−0.0072 (8)
C10	0.0667 (12)	0.0472 (10)	0.0599 (11)	0.0112 (9)	−0.0026 (9)	−0.0058 (9)
C11	0.0630 (12)	0.0580 (12)	0.0595 (11)	0.0127 (10)	−0.0142 (9)	−0.0045 (10)
C12	0.0580 (11)	0.0560 (11)	0.0426 (9)	0.0020 (9)	−0.0108 (8)	−0.0054 (8)
C13	0.0469 (9)	0.0403 (9)	0.0341 (8)	−0.0035 (7)	0.0008 (6)	−0.0004 (7)
C14	0.0528 (9)	0.0442 (9)	0.0320 (7)	−0.0032 (8)	0.0006 (6)	−0.0015 (7)
N1S	0.0525 (9)	0.0487 (9)	0.0438 (8)	−0.0061 (8)	−0.0055 (7)	0.0056 (7)
C2S	0.0531 (10)	0.0462 (9)	0.0368 (8)	−0.0016 (8)	0.0000 (7)	0.0001 (7)

Geometric parameters (Å, º) top

O1—C7	1.235 (2)	C8—C9	1.388 (2)
O2—C14	1.268 (2)	C8—C13	1.412 (2)
O3—C14	1.2523 (18)	C9—C10	1.377 (2)
N1—C7	1.3474 (19)	C9—H9	0.9300
N1—C8	1.406 (2)	C10—C11	1.380 (2)
N1—H1	0.90 (2)	C10—H10	0.9300
C1—C2	1.382 (3)	C11—C12	1.378 (3)
C1—C6	1.386 (2)	C11—H11	0.9300
C1—C7	1.495 (2)	C12—C13	1.388 (2)
C2—C3	1.393 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.508 (2)
C3—C4	1.377 (3)	N1S—C2S	1.483 (2)
C3—H3	0.9300	N1S—H1A	0.940 (15)
C4—C5	1.367 (3)	N1S—H1B	0.983 (16)
C4—H4	0.9300	N1S—H1C	0.936 (15)
C5—C6	1.376 (3)	C2S—C2Sⁱ	1.501 (3)
C5—H5	0.9300	C2S—H2A	0.9700
C6—H6	0.9300	C2S—H2B	0.9700

C7—N1—C8	129.24 (16)	C8—C9—H9	119.7
C7—N1—H1	120.3 (13)	C9—C10—C11	120.70 (18)
C8—N1—H1	110.4 (13)	C9—C10—H10	119.7
C2—C1—C6	119.29 (18)	C11—C10—H10	119.7
C2—C1—C7	123.45 (15)	C12—C11—C10	119.03 (17)
C6—C1—C7	117.25 (17)	C12—C11—H11	120.5
C1—C2—C3	120.02 (18)	C10—C11—H11	120.5
C1—C2—H2	120.0	C11—C12—C13	122.03 (16)
C3—C2—H2	120.0	C11—C12—H12	119.0
C4—C3—C2	119.7 (2)	C13—C12—H12	119.0
C4—C3—H3	120.1	C12—C13—C8	118.15 (16)
C2—C3—H3	120.1	C12—C13—C14	117.66 (14)
C5—C4—C3	120.3 (2)	C8—C13—C14	124.19 (14)
C5—C4—H4	119.9	O3—C14—O2	122.25 (16)
C3—C4—H4	119.9	O3—C14—C13	118.66 (15)
C4—C5—C6	120.3 (2)	O2—C14—C13	119.07 (14)
C4—C5—H5	119.8	C2S—N1S—H1A	111.1 (12)
C6—C5—H5	119.8	C2S—N1S—H1B	112.5 (14)
C5—C6—C1	120.3 (2)	H1A—N1S—H1B	105.2 (18)
C5—C6—H6	119.8	C2S—N1S—H1C	110.9 (13)
C1—C6—H6	119.8	H1A—N1S—H1C	113.1 (19)
O1—C7—N1	124.08 (17)	H1B—N1S—H1C	103.8 (19)
O1—C7—C1	120.75 (14)	N1S—C2S—C2Sⁱ	110.32 (17)
N1—C7—C1	115.16 (15)	N1S—C2S—H2A	109.6
C9—C8—N1	122.83 (15)	C2Sⁱ—C2S—H2A	109.6
C9—C8—C13	119.58 (15)	N1S—C2S—H2B	109.6
N1—C8—C13	117.55 (15)	C2Sⁱ—C2S—H2B	109.6
C10—C9—C8	120.52 (16)	H2A—C2S—H2B	108.1
C10—C9—H9	119.7

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.90 (2)	1.81 (2)	2.608 (2)	146.8 (19)
N1s—H1A···O1	0.94 (2)	1.89 (2)	2.807 (2)	165 (2)
N1s—H1B···O3ⁱⁱ	0.98 (2)	1.76 (2)	2.729 (2)	170 (2)
N1s—H1C···O2ⁱⁱⁱ	0.94 (2)	1.84 (2)	2.753 (2)	163 (2)
C2s—H2B···O3^iv	0.97	2.59	3.315 (2)	131
C6—H6···O3^iv	0.93	2.50	3.319 (2)	147
C9—H9···O1	0.93	2.25	2.863 (2)	123
C12—H12···O3	0.93	2.42	2.758 (2)	101

Symmetry codes: (ii) −x+5/2, y−1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.90 (2)	1.81 (2)	2.608 (2)	146.8 (19)
N1s—H1A···O1	0.94 (2)	1.89 (2)	2.807 (2)	165.1 (18)
N1s—H1B···O3ⁱ	0.98 (2)	1.76 (2)	2.729 (2)	170.4 (19)
N1s—H1C···O2ⁱⁱ	0.94 (2)	1.84 (2)	2.753 (2)	163 (2)
C2s—H2B···O3ⁱⁱⁱ	0.97	2.59	3.315 (2)	131
C6—H6···O3ⁱⁱⁱ	0.93	2.50	3.319 (2)	147
C9—H9···O1	0.93	2.25	2.863 (2)	123
C12—H12···O3	0.93	2.42	2.758 (2)	101

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

This work was supported by a Grant for Fundamental Research from the Center of Science and Technology, Uzbekistan (No. FA–F3–T-141).

References

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