1,3-Phenyl­enediammonium dinitrate

Abstract

In the title compound, C₆H₁₀N₂ ²⁺·2NO₃ ⁻, the dication lies on a crystallographic twofold rotation axis. The nitrate ions are linked to the dications though N—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For general background to polyamines, see: Bianchi et al. (1997 ▶); Ilioudis et al. (2002 ▶); Hossain (2008 ▶). For related structures, see: Anderson et al. (2006 ▶; Gawlicka-Chruszcz & Stadnicka (2002 ▶); Soumhi & Jouini (1995 ▶); Wang et al. (2007 ▶).

Experimental

Crystal data

• C₆H₁₀N₂ ²⁺·2NO₃ ⁻

• M _r = 234.18

• Monoclinic,

• a = 16.2548 (12) Å

• b = 9.6212 (8) Å

• c = 7.1070 (6) Å

• β = 115.506 (6)°

• V = 1003.14 (14) ų

• Z = 4

• Cu Kα radiation

• μ = 1.22 mm⁻¹

• T = 100 K

• 0.53 × 0.50 × 0.24 mm

Data collection

• Bruker APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.562, T _max = 0.761

• 5278 measured reflections

• 942 independent reflections

• 882 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.092

• S = 1.01

• 942 reflections

• 84 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.26 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

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
N5—H5A⋯O1A	0.94 (2)	1.87 (2)	2.7955 (15)	168 (2)
N5—H5B⋯O1Ai	0.92 (2)	1.95 (2)	2.8416 (16)	163 (2)
N5—H5C⋯O3Aii	0.92 (2)	1.96 (2)	2.8626 (16)	167 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Simple polyammonium ions are known as excellent hydrogen bond donors for a variety of anions in particular for oxoanions, forming supramolecular aggregates with hydrogen bonding networks (Ilioudis et al., 2002). Indeed, a difunctional or trifunctional polyamine is widely used as an essential building block for a macrocyclic based host, and acts as major binding components for a negatively charged anion (Bianchi et al., 1997; Hossain, 2008). In this study, we used a simple 1,3-phenylenediamine to prepare an adduct with nitric acid. We report, herein, the crystal structure of the title compound in which the nitrate anions are connected to the cationic units through hydrogen bonding interactions.

X-ray analysis of the nitrate salt reveals that both amino groups are protonated to form a dication and crystallized with two nitrate anions. In the crystal lattice, each diaction is surrounded by two symmetry related nitrate anions (Fig. 1). Each amino group is engaged in coordinating nitrate anions through N—H ···O bonds ranging from 2.7955 (15) to 2.8626 (16) Å (see Table 1). The crystal structure viewed along the b axis shows that the cations are arranged antiparallel to one another along the c axis in which two adjacent aromatic units are separated at 7.024 Å (Fig. 2). Therefore, there is no π-π stacking involved. The nitrates serve as linkers of the two adjacent aromatic units by hydrogen bonding networks along the b axis.

Experimental

To a solution of 1,3-phenylenediamine (0.1 g) in CH₃OH (2 ml) was added a few drop of nitric acid. The white precipitate formed immediately was filtered and washed with diethyl ether. Yield: 80%. M.P. 150.5°C. ¹H NMR (500 MHz, D₂O, TSP): δ 7.15 (m, J = 4 Hz,1H, ArH), 6.68 (d, J = 8 Hz, J = 2 Hz, 2H, ArH), 6.62 (t, J= 2 Hz, 1H, ArH). Crystals suitable for X-ray crystallography were obtained by recystallization from a methanolic solution of the salt and isolated after seven days keeping the solution under Et₂O diffusion in a desiccator.

Refinement

H atoms bonded to carbons were positioned geometrically and refined using a riding model, with C-H = 0.99 Å and U_iso(H) = 1.2 U_eq(C). H atoms bonded to N atoms were located in a difference map and their positional parameters were refined, with U_iso(H) = 1.2 U_eq(N).

Figures

Fig. 1.

The formula unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonding interactions. Symmetry code: (i) -x, y, 1/2 -z.

Fig. 2.

Crystal packing of the title compound, viewed along the b axis.

Crystal data

C6H10N22+·2NO3−	F(000) = 488
Mr = 234.18	Dx = 1.551 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 3468 reflections
a = 16.2548 (12) Å	θ = 5.5–69.5°
b = 9.6212 (8) Å	µ = 1.22 mm−1
c = 7.1070 (6) Å	T = 100 K
β = 115.506 (6)°	Block, colorless
V = 1003.14 (14) Å3	0.53 × 0.50 × 0.24 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	942 independent reflections
Radiation source: fine-focus sealed tube	882 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 69.5°, θmin = 5.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −19→18
Tmin = 0.562, Tmax = 0.761	k = −11→11
5278 measured reflections	l = −8→8

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.054P)2 + 1.07P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
942 reflections	Δρmax = 0.26 e Å−3
84 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (5)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.16571 (7)	0.19642 (12)	1.08086 (17)	0.0129 (3)
O1A	0.11343 (7)	0.11334 (11)	0.94063 (14)	0.0171 (3)
O2A	0.17425 (7)	0.31761 (10)	1.03487 (16)	0.0205 (3)
O3A	0.20794 (7)	0.15171 (11)	1.26369 (14)	0.0170 (3)
C1	0.0000	0.16909 (19)	0.2500	0.0119 (4)
H1	0.0000	0.0703	0.2500	0.014*
C2	0.06684 (9)	0.24329 (14)	0.40956 (19)	0.0125 (3)
C3	0.06855 (9)	0.38745 (15)	0.4119 (2)	0.0148 (3)
H3	0.1156	0.4364	0.5218	0.018*
C4	0.0000	0.4588 (2)	0.2500	0.0167 (4)
H4	0.0000	0.5575	0.2500	0.020*
N5	0.13746 (8)	0.16679 (12)	0.58086 (17)	0.0136 (3)
H5A	0.1261 (12)	0.1620 (17)	0.700 (3)	0.016*
H5B	0.1409 (11)	0.079 (2)	0.535 (3)	0.016*
H5C	0.1918 (13)	0.2147 (19)	0.624 (3)	0.016*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1A	0.0125 (6)	0.0140 (6)	0.0121 (6)	0.0001 (4)	0.0053 (4)	−0.0013 (4)
O1A	0.0187 (5)	0.0179 (5)	0.0115 (5)	−0.0058 (4)	0.0034 (4)	−0.0038 (4)
O2A	0.0234 (6)	0.0108 (5)	0.0243 (6)	−0.0001 (4)	0.0075 (4)	0.0016 (4)
O3A	0.0154 (5)	0.0232 (6)	0.0100 (5)	−0.0005 (4)	0.0032 (4)	0.0017 (4)
C1	0.0139 (9)	0.0107 (9)	0.0117 (9)	0.000	0.0062 (7)	0.000
C2	0.0122 (7)	0.0161 (7)	0.0097 (6)	0.0005 (5)	0.0053 (5)	0.0011 (5)
C3	0.0157 (7)	0.0151 (7)	0.0138 (7)	−0.0031 (5)	0.0065 (6)	−0.0034 (5)
C4	0.0215 (10)	0.0119 (9)	0.0191 (9)	0.000	0.0112 (8)	0.000
N5	0.0133 (6)	0.0149 (6)	0.0098 (6)	−0.0005 (4)	0.0022 (5)	−0.0005 (4)

Geometric parameters (Å, °)

N1A—O2A	1.2348 (16)	C3—C4	1.3901 (16)
N1A—O3A	1.2556 (15)	C3—H3	0.95
N1A—O1A	1.2747 (15)	C4—H4	0.95
C1—C2	1.3838 (16)	N5—H5A	0.943 (19)
C1—H1	0.95	N5—H5B	0.92 (2)
C2—C3	1.387 (2)	N5—H5C	0.924 (19)
C2—N5	1.4621 (16)
O2A—N1A—O3A	121.59 (11)	C4—C3—H3	120.7
O2A—N1A—O1A	119.88 (11)	C3i—C4—C3	120.83 (18)
O3A—N1A—O1A	118.53 (11)	C3—C4—H4	119.6
C2i—C1—C2	117.89 (17)	C2—N5—H5A	112.7 (10)
C2—C1—H1	121.1	C2—N5—H5B	108.4 (11)
C1—C2—C3	122.02 (12)	H5A—N5—H5B	109.8 (14)
C1—C2—N5	118.72 (13)	C2—N5—H5C	108.7 (11)
C3—C2—N5	119.26 (11)	H5A—N5—H5C	104.8 (15)
C2—C3—C4	118.62 (12)	H5B—N5—H5C	112.5 (15)
C2—C3—H3	120.7
C2i—C1—C2—C3	−0.49 (9)	N5—C2—C3—C4	−178.80 (10)
C2i—C1—C2—N5	179.28 (13)	C2—C3—C4—C3i	−0.47 (8)
C1—C2—C3—C4	0.97 (17)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1A	0.94 (2)	1.87 (2)	2.7955 (15)	168 (2)
N5—H5B···O1Aii	0.92 (2)	1.95 (2)	2.8416 (16)	163 (2)
N5—H5C···O3Aiii	0.92 (2)	1.96 (2)	2.8626 (16)	167 (2)

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