1,3-Phenyl­enediammonium dinitrate

Portis, B.; Dey, K.R.; Saeed, M.A.; Powell, D.R.; Hossain, M.A.

doi:10.1107/S1600536809039166

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2601

https://doi.org/10.1107/S1600536809039166

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1,3-Phenylenediammonium dinitrate

Bobby Portis,^a Kalpana R. Dey,^a Musabbir A. Saeed,^a Douglas R. Powell ^b and Md. Alamgir Hossain ^a ^*

^aDepartment of Chemistry and Biochemistry, 1400 J. R. Lynch St, PO Box 17910, Jackson State University, Jackson, MS 39217-0510, USA, and ^bDepartment of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Room 208, Norman, OK 73019-3051, USA
^*Correspondence e-mail: alamgir@chem.jsums.edu

(Received 22 September 2009; accepted 26 September 2009; online 3 October 2009)

In the title compound, C₆H₁₀N₂²⁺·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

C₆H₁₀N₂²⁺·2NO₃⁻
M_r = 234.18
Monoclinic, C 2/c
a = 16.2548 (12) Å
b = 9.6212 (8) Å
c = 7.1070 (6) Å
β = 115.506 (6)°
V = 1003.14 (14) Å³
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[F² > 2σ(F²)] = 0.033
wR(F²) = 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

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) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809039166/ci2920sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039166/ci2920Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

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

Figures top

	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.

1,3-Phenylenediammonium dinitrate top

Crystal data top

C₆H₁₀N₂²⁺·2NO₃⁻	F(000) = 488
M_r = 234.18	D_x = 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 top

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

Refinement top

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(F_o²) + (0.054P)² + 1.07P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
942 reflections	Δρ_max = 0.26 e Å⁻³
84 parameters	Δρ_min = −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)

Crystal data top

C₆H₁₀N₂²⁺·2NO₃⁻	V = 1003.14 (14) Å³
M_r = 234.18	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 16.2548 (12) Å	µ = 1.22 mm⁻¹
b = 9.6212 (8) Å	T = 100 K
c = 7.1070 (6) Å	0.53 × 0.50 × 0.24 mm
β = 115.506 (6)°

Data collection top

Bruker APEX CCD area-detector diffractometer	942 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	882 reflections with I > 2σ(I)
T_min = 0.562, T_max = 0.761	R_int = 0.036
5278 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.26 e Å⁻³
942 reflections	Δρ_min = −0.20 e Å⁻³
84 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₂²⁺·2NO₃⁻
M_r	234.18
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	16.2548 (12), 9.6212 (8), 7.1070 (6)
β (°)	115.506 (6)
V (Å³)	1003.14 (14)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.53 × 0.50 × 0.24

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.562, 0.761
No. of measured, independent and observed [I > 2σ(I)] reflections	5278, 942, 882
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.01
No. of reflections	942
No. of parameters	84
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) x, −y, z−1/2; (ii) −x+1/2, −y+1/2, −z+2.

Acknowledgements

This work was supported by the National Center for Research Resources (grant No. G12RR013459) and the National Institutes of Health (NIH) Science Education Partnership Award (SEPA) Program `Recovery Act Administrative Supplements Providing Summer Research Research Experiences for Students and Science Educators' under contract 5R25RR020405–04S1. Funds to purchase the diffractometer used in this study were provided in part by the National Science Foundation (grant No. CHE-0130835).

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