Ethyl­enediaminium dinicotinate

Abstract

In the title compound, C₂H₁₀N₂ ²⁺·2C₆H₄NO₂ ⁻, the cation lies on an inversion centre. The asymmetric unit is composed of one nicotinate anion and one half ethyl­enediaminium cation. All the amino H atoms are involved in N—H⋯O and N—H⋯N hydrogen bonds. These hydrogen bonds link the ionic units into a three-dimensional network. In addition, π–π inter­actions between pyridine rings [centroid–centroid distance = 3.6037 (7) Å] further stabilize the crystal structure.

Related literature

For applications of amino compounds, see: Fu et al. (2010 ▶); Aminabhavi et al. (1986 ▶).

Experimental

Crystal data

• C₂H₁₀N₂ ²⁺·2C₆H₄NO₂ ⁻

• M _r = 306.32

• Monoclinic,

• a = 6.2953 (13) Å

• b = 16.835 (3) Å

• c = 6.8288 (14) Å

• β = 102.03 (3)°

• V = 707.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 298 K

• 0.30 × 0.05 × 0.05 mm

Data collection

• Rigaku Mercury2 diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.910, T _max = 1.000

• 7181 measured reflections

• 1618 independent reflections

• 1162 reflections with I > 2σ(I)

• R _int = 0.056

Refinement

• R[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 0.147

• S = 1.08

• 1618 reflections

• 101 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811023877/bx2355Isup3.cml

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
N1—H1B⋯N2i	0.90	2.24	2.971 (3)	138
N1—H1C⋯O1ii	0.90	1.85	2.729 (3)	164
N1—H1A⋯O2	0.90	1.83	2.711 (3)	166

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The amino derivatives have found wide range of applications in material science, such as magnetic, fluorescent and dielectric behaviors, and there has been an increased interest motif in the preparation of amino cocrystal compounds (Aminabhavi et al., 1986; Fu, et al. 2010). We report here the crystal structure of the title compound. In the title compound, [(C₂H₁₀N₂)(C₆H₄NO₂)₂], the cation lies on inversion centre. The asymmetric unit is composed of one nicotinate anion and one-half ethylenediaminium cation, (Fig.1). Both the amine N atoms of the ethylenediaminium cation are protonated. The geometric parameters are in the normal range. In the crystal structure, all the amino group H atoms are involved in N—H···O and N—H···N hydrogen bonds (Table1). These hydrogen bonds link the ionic units into a three-dimentional network. In addition, the pyridine rings π–π (centroid-to-centroid distance = 3.6037 (7) Å, symmetry code: x, 1/2-y, 1/2+z) interactions further stabilized the structure (Fig. 2).

Experimental

A mixture of ethylenediamine (0.4 mmol) and nicotinic acid (0.8 mmol) were dissolved in distilled water (10 ml). Colorless block crystals suitable for X-ray analysis were obtained after 3 days.

Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C— H = 0.97 Å(methylene) and C— H = 0.93 Å(aromatic) with U_iso(H) = 1.2U_eq(C). The positional parameters of the H atoms (N1) were refined freely, in the last stage of the refinement, it were restrained with the H—N = 0.90 (2) Å, with U_iso(H) = 1.5U_eq(N).

Figures

Fig. 1.

Molecular view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The crystal packing of the title compound viewed along the c axis showing the one-dimensionnal hydrogen bondings chain (dashed line). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C2H10N22+·2C6H4NO2−	F(000) = 324
Mr = 306.32	Dx = 1.437 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1618 reflections
a = 6.2953 (13) Å	θ = 3.3–27.5°
b = 16.835 (3) Å	µ = 0.11 mm−1
c = 6.8288 (14) Å	T = 298 K
β = 102.03 (3)°	Block, colourless
V = 707.8 (3) Å3	0.30 × 0.05 × 0.05 mm
Z = 2

Data collection

Rigaku Mercury2 diffractometer	1618 independent reflections
Radiation source: fine-focus sealed tube	1162 reflections with I > 2σ(I)
graphite	Rint = 0.056
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.3°
CCD profile fitting scans	h = −7→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→21
Tmin = 0.910, Tmax = 1.000	l = −8→8
7181 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062	H-atom parameters constrained
wR(F2) = 0.147	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.4625P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
1618 reflections	Δρmax = 0.23 e Å−3
101 parameters	Δρmin = −0.25 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (6)

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 > 2sigma(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	0.0882 (3)	0.56578 (10)	0.8189 (3)	0.0407 (5)
O2	0.4172 (3)	0.61799 (10)	0.9019 (3)	0.0415 (5)
C2	0.1214 (3)	0.70652 (13)	0.8166 (3)	0.0226 (5)
N1	0.6707 (3)	0.51198 (11)	0.7583 (3)	0.0284 (5)
H1A	0.5813	0.5405	0.8182	0.043*
H1B	0.6812	0.4603	0.7926	0.043*
H1C	0.8057	0.5313	0.8016	0.043*
N2	0.1923 (3)	0.84765 (12)	0.8146 (3)	0.0366 (5)
C3	−0.0997 (4)	0.72136 (13)	0.7603 (4)	0.0284 (5)
H3A	−0.1982	0.6795	0.7416	0.034*
C5	−0.0222 (4)	0.85903 (14)	0.7611 (4)	0.0346 (6)
H5A	−0.0727	0.9110	0.7423	0.042*
C1	0.2585 (4)	0.77203 (14)	0.8423 (4)	0.0308 (6)
H1D	0.4069	0.7628	0.8816	0.037*
C6	0.2143 (3)	0.62372 (13)	0.8475 (3)	0.0248 (5)
C7	0.6080 (4)	0.52001 (14)	0.5385 (3)	0.0278 (5)
H7B	0.7182	0.4959	0.4773	0.033*
H7A	0.5977	0.5758	0.5025	0.033*
C4	−0.1726 (4)	0.79878 (14)	0.7320 (4)	0.0326 (6)
H4A	−0.3202	0.8098	0.6942	0.039*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0329 (10)	0.0209 (9)	0.0674 (13)	−0.0021 (7)	0.0086 (9)	−0.0007 (8)
O2	0.0237 (9)	0.0340 (10)	0.0633 (13)	0.0046 (7)	0.0006 (8)	−0.0115 (9)
C2	0.0247 (11)	0.0225 (11)	0.0210 (11)	−0.0010 (9)	0.0058 (9)	−0.0012 (9)
N1	0.0268 (10)	0.0222 (10)	0.0342 (11)	0.0025 (8)	0.0016 (8)	−0.0010 (8)
N2	0.0402 (12)	0.0247 (11)	0.0466 (13)	−0.0054 (9)	0.0128 (10)	−0.0029 (9)
C3	0.0278 (12)	0.0223 (12)	0.0346 (13)	−0.0024 (9)	0.0050 (10)	−0.0004 (10)
C5	0.0485 (15)	0.0214 (13)	0.0370 (14)	0.0037 (11)	0.0158 (12)	0.0031 (10)
C1	0.0262 (12)	0.0286 (13)	0.0383 (14)	−0.0031 (10)	0.0081 (10)	−0.0022 (10)
C6	0.0257 (12)	0.0234 (12)	0.0253 (12)	0.0000 (9)	0.0057 (9)	−0.0028 (9)
C7	0.0266 (12)	0.0236 (12)	0.0326 (13)	−0.0029 (9)	0.0048 (10)	0.0022 (10)
C4	0.0299 (13)	0.0308 (13)	0.0370 (14)	0.0047 (10)	0.0069 (11)	0.0044 (11)

Geometric parameters (Å, °)

O1—C6	1.247 (3)	N2—C1	1.341 (3)
O2—C6	1.257 (3)	C3—C4	1.382 (3)
C2—C3	1.387 (3)	C3—H3A	0.9300
C2—C1	1.389 (3)	C5—C4	1.373 (3)
C2—C6	1.509 (3)	C5—H5A	0.9300
N1—C7	1.476 (3)	C1—H1D	0.9300
N1—H1A	0.9005	C7—C7i	1.510 (4)
N1—H1B	0.9004	C7—H7B	0.9700
N1—H1C	0.9004	C7—H7A	0.9700
N2—C5	1.337 (3)	C4—H4A	0.9300
C3—C2—C1	116.9 (2)	N2—C1—C2	124.7 (2)
C3—C2—C6	122.82 (19)	N2—C1—H1D	117.6
C1—C2—C6	120.2 (2)	C2—C1—H1D	117.6
C7—N1—H1A	110.7	O1—C6—O2	124.1 (2)
C7—N1—H1B	110.0	O1—C6—C2	119.0 (2)
H1A—N1—H1B	114.6	O2—C6—C2	116.87 (19)
C7—N1—H1C	109.6	N1—C7—C7i	110.1 (2)
H1A—N1—H1C	107.1	N1—C7—H7B	109.6
H1B—N1—H1C	104.5	C7i—C7—H7B	109.6
C5—N2—C1	116.2 (2)	N1—C7—H7A	109.6
C4—C3—C2	119.6 (2)	C7i—C7—H7A	109.6
C4—C3—H3A	120.2	H7B—C7—H7A	108.2
C2—C3—H3A	120.2	C5—C4—C3	118.5 (2)
N2—C5—C4	124.1 (2)	C5—C4—H4A	120.7
N2—C5—H5A	118.0	C3—C4—H4A	120.7
C4—C5—H5A	118.0
C1—C2—C3—C4	0.2 (3)	C3—C2—C6—O1	1.0 (3)
C6—C2—C3—C4	−179.1 (2)	C1—C2—C6—O1	−178.3 (2)
C1—N2—C5—C4	−0.7 (4)	C3—C2—C6—O2	−178.8 (2)
C5—N2—C1—C2	1.0 (4)	C1—C2—C6—O2	1.9 (3)
C3—C2—C1—N2	−0.7 (4)	N2—C5—C4—C3	0.3 (4)
C6—C2—C1—N2	178.6 (2)	C2—C3—C4—C5	0.0 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2ii	0.90	2.24	2.971 (3)	138
N1—H1C···O1iii	0.90	1.85	2.729 (3)	164
N1—H1A···O2	0.90	1.83	2.711 (3)	166

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