o-Phenyl­enediaminium chloride nitrate

Soudani, S.; Kefi, R.; Jelsch, C.; Wenger, E.; Ben Nasr, C.

doi:10.1107/S1600536813007447

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o600

doi:10.1107/S1600536813007447

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o-Phenylenediaminium chloride nitrate

Sarra Soudani,^a Riadh Kefi,^a Christian Jelsch,^b Emmanuel Wenger ^b and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, and ^bCristallographie, Résonance Magnétique et Modélisations (CRM2), UMR CNRS–UHP 7036, Institut Jean Barriol, Université de Lorraine, BP 70239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 4 March 2013; accepted 18 March 2013; online 28 March 2013)

In the title molecular salt, C₆H₁₀N₂²⁺·NO₃⁻·Cl⁻, the complete cation is generated by a crystallographic mirror plane. The complete nitrate ion is also generated by reflection, with the N atom and one O atom lying on the mirror plane; the chloride ion also lies on the reflection plane. In the crystal, the components are linked by N—H⋯Cl and N—H⋯(N,O) hydrogen bonds, forming (001) layers with the benzene rings projecting into the interlayer regions. The layers are linked by weak C—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For background to inorganic–organic hybrid compounds, see: Bringley & Rajeswaram (2006 ); Dai et al. (2002 ). For reference structural data, see: Riahi et al. (2012 ); Engh & Huber (1991 ).

Experimental

Crystal data

C₆H₁₀N₂²⁺·Cl⁻·NO₃⁻
M_r = 207.61
Orthorhombic, P n m a
a = 7.3695 (5) Å
b = 8.2367 (5) Å
c = 14.2398 (7) Å
V = 864.36 (8) Å³
Z = 4
Ag Kα radiation
λ = 0.56085 Å
μ = 0.22 mm⁻¹
T = 100 K
0.27 × 0.20 × 0.15 mm

Data collection

Bruker Photon100 CMOS detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.751, T_max = 0.967
26823 measured reflections
812 independent reflections
812 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.053
S = 0.80
812 reflections
66 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H34⋯O10	1.033 (4)	2.41 (1)	2.896 (2)	107.4 (9)
N3—H34⋯N1	1.033 (4)	2.429 (9)	3.263 (2)	137.1 (8)
N3—H31⋯Cl1ⁱ	1.033 (4)	2.181 (4)	3.179 (2)	161.8 (5)
N3—H32⋯Cl1	1.033 (4)	2.183 (5)	3.156 (2)	156.2 (5)
C2—H2⋯O11	1.08	2.48	3.299 (2)	132
C1—H1⋯O10ⁱⁱ	1.08	2.52	3.427 (2)	141
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

Data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: MoPro (Jelsch et al., 2005 ); molecular graphics: DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813007447/hb7052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813007447/hb7052Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813007447/hb7052Isup3.cml

checkCIF report

Comment top

Inorganic-organic hybrid compounds provide a class of materials with interesting potential technological applications (Bringley & Rajeswaram 2006; Dai et al., 2002). As part of our studies in this area, we report here the synthesis and the crystal structure of the title compound, (I), formed by the reaction between benzene-1,2-diamine, nitric acid and hydrochloric acid. The structure consists of one nitrate anion, one chloride anion and one benzene-1,2-diaminium dication (Fig. 1). In the crystal, the H atoms of the ammonium groups are involved in two kinds of hydrogen bonds: N—H···Cl and N3—H34···(N1, O10), which is a bifurcated H-bond interaction (Table 1). These hydrogen bonds link the ionic units (NH₃⁺, Cl^- and NO₃^-) into layers parallel to (001) (Fig. 2) and situated at z = n +/- 1/4 (Fig. 3). The chloride ion is actually located on a special position with y = 1/4. The phenyl groups of the benzene-1,2-diaminium dications are located alternatively on either side of the ionic layers via three weak C—H···O hydrogen bonds (Fig. 3) with the nitrate anion, which is perpendicular to the phenyl plane. No π-π stacking interactions between the organic rings or C—H···π interactions towards them are observed.

The geometrical parameters of the title compound are in the normal range. A N—O moiety of the nitrate is located on a special position y=3/4 and the two independant N—O bond distances are 1.243 (2) and 1.284 (1) Å. In addition, the O—N—O bond angle values are 118.6 (2)° and 122.8 (2), showing that the nitrate anion exhibits a slightly distorted C_{3 h} geometry. These anionic geometrical features are comparable to those previously reported for 2-cyanoanilinium nitrate where the N—O bond length distances are in the range 1.228 (2)–1.273 (2) Å and the values of the O—N—O angles are between 117.52 (2) and 121,80 (15)° (Riahi et al., 2012). For the organic cation, the mean value of the C—C bond lengths of the aromatic ring is 1.391 (2) Å which is close to the 1.382 (3) value between >CH aromatic atoms in the Engh & Huber (1991) stereochemical dictionary.

Related literature top

For background to inorganic–organic hybrid compounds, see: Bringley & Rajeswaram (2006); Dai et al. (2002). For reference structural data, see: Riahi et al. (2012); Engh & Huber (1991).

Experimental top

A mixture of an aqueous solution of benzene-1,2-diamine (3 mmol), nitric acid (3 mmol) and hydrochloric acid (3 mmol) was slowly evaporated at room temperature over several days leading to formation of transparent light brown prismatic crystals (yield 60%). The crystals are stable for months under normal conditions of temperature and humidity.

Computing details top

Data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: MoPro (Jelsch et al., 2005); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the title compound, showing 50% probability displacement ellipsoids and spheres for the H atoms. Symmetry codes: (i) x, 1/2-y, z; (ii) x, 3/2-y, z.
	Fig. 2. Projection along the c-axis of the inorganic layers in the structure of the title compound. Hydrogen bonds are shown as broken lines.
	Fig. 3. The packing diagram of the compound viewed down the b-axis. Hydrogen bonds are shown as broken lines.

o-Phenylenediaminium chloride nitrate top

Crystal data top

C₆H₁₀N₂²⁺·Cl⁻·NO₃⁻	F(000) = 432
M_r = 207.61	D_x = 1.596 Mg m⁻³
Orthorhombic, Pnma	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2ac 2n	Cell parameters from 64 reflections
a = 7.3695 (5) Å	θ = 3.1–20.3°
b = 8.2367 (5) Å	µ = 0.22 mm⁻¹
c = 14.2398 (7) Å	T = 100 K
V = 864.36 (8) Å³	Prismatic, yellow
Z = 4	0.27 × 0.20 × 0.15 mm

Data collection top

Bruker Photon100 CMOS detector diffractometer	812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
ω scans	θ_max = 19.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = 0→8
T_min = 0.751, T_max = 0.967	k = 0→9
26823 measured reflections	l = 0→16
812 independent 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ²(F_o²) + (0.P)² + 2.3P] where P = (F_o² + 2F_c²)/3
812 reflections	(Δ/σ)_max = −0.002
66 parameters	Δρ_max = 0.27 e Å⁻³
12 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₆H₁₀N₂²⁺·Cl⁻·NO₃⁻	V = 864.36 (8) Å³
M_r = 207.61	Z = 4
Orthorhombic, Pnma	Ag Kα radiation, λ = 0.56085 Å
a = 7.3695 (5) Å	µ = 0.22 mm⁻¹
b = 8.2367 (5) Å	T = 100 K
c = 14.2398 (7) Å	0.27 × 0.20 × 0.15 mm

Data collection top

Bruker Photon100 CMOS detector diffractometer	812 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	812 reflections with I > 2σ(I)
T_min = 0.751, T_max = 0.967	R_int = 0.049
26823 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	12 restraints
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	Δρ_max = 0.27 e Å⁻³
812 reflections	Δρ_min = −0.26 e Å⁻³
66 parameters

Special details top

Refinement. Refinement of F² against reflections. The threshold expression of F² > 2sigma(F²) is used for calculating R-factors(gt) 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
Cl1	0.84182 (9)	0.25000	0.34646 (4)	0.00937 (9)
N1	0.2199 (3)	0.75000	0.3046 (2)	0.0091 (3)
O11	0.3554 (3)	0.75000	0.3614 (1)	0.0098 (3)
O10	0.1566 (2)	0.6174 (2)	0.27870 (9)	0.0143 (2)
C1	0.1707 (3)	0.3346 (2)	0.5526 (1)	0.0117 (3)
H1	0.10400	0.40337	0.60752	0.01410*
C2	0.2654 (3)	0.4193 (2)	0.4834 (1)	0.0100 (2)
H2	0.26439	0.55074	0.48291	0.01199*
C3	0.3611 (2)	0.3345 (2)	0.4152 (1)	0.0071 (2)
N3	0.4604 (2)	0.4241 (2)	0.3431 (1)	0.0083 (2)
H31	0.417 (1)	0.393 (1)	0.2766 (3)	0.01240*
H32	0.5979 (4)	0.400 (1)	0.3466 (10)	0.01240*
H34	0.443 (2)	0.5479 (3)	0.3506 (9)	0.01240*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0105 (3)	0.0079 (3)	0.0097 (3)	0	−0.0003 (3)	0
N1	0.011 (1)	0.006 (1)	0.010 (1)	0	−0.0011 (9)	0
O11	0.0117 (9)	0.0032 (9)	0.0145 (10)	0	−0.0032 (8)	0
O10	0.0168 (7)	0.0076 (6)	0.0184 (7)	−0.0016 (6)	−0.0052 (6)	−0.0023 (6)
C1	0.0149 (9)	0.0101 (10)	0.0102 (9)	0.0008 (8)	0.0030 (8)	−0.0012 (8)
C2	0.0128 (9)	0.0058 (9)	0.0113 (9)	0.0008 (8)	0.0011 (7)	−0.0014 (7)
C3	0.0084 (9)	0.0052 (9)	0.0079 (9)	−0.0001 (8)	0.0010 (7)	0.0003 (7)
N3	0.0099 (8)	0.0049 (7)	0.0100 (7)	−0.0008 (6)	0.0002 (6)	0.0008 (6)

Geometric parameters (Å, º) top

N1—O10	1.243 (2)	C2—H2	1.083
N1—O11	1.284 (3)	C3—N3	1.461 (2)
C1—C2	1.395 (3)	N3—H32	1.033 (4)
C1—H1	1.083	N3—H34	1.033 (4)
C2—C3	1.389 (3)	N3—H31	1.033 (4)

O11—N1—O10	118.6 (2)	C3—N3—H32	111.2 (7)
O10—N1—O10ⁱ	122.8 (2)	C3—N3—H34	111.3 (7)
C1—C2—C3	119.8 (2)	C3—N3—H31	111.1 (6)
C1—C2—H2	120.1	H31—N3—H32	107.7 (8)
H1—C1—C2	118.4	H31—N3—H34	107.6 (9)
C2—C3—N3	119.5 (2)	H32—N3—H34	107.7 (10)
H2—C2—C3	120.1

C1—C2—C3—N3	−179.8 (2)	C2—C3—N3—H34	−2.1 (7)
H1—C1—C2—C3	176.3	C2—C3—N3—H31	−122.0 (7)
H1—C1—C2—H2	−3.7	H2—C2—C3—N3	0.2
C2—C3—N3—H32	118.0 (8)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H34···O10	1.033 (4)	2.41 (1)	2.896 (2)	107.4 (9)
N3—H34···N1	1.033 (4)	2.429 (9)	3.263 (2)	137.1 (8)
N3—H31···Cl1ⁱⁱ	1.033 (4)	2.181 (4)	3.179 (2)	161.8 (5)
N3—H32···Cl1	1.033 (4)	2.183 (5)	3.156 (2)	156.2 (5)
C2—H2···O11	1.08	2.48	3.299 (2)	132
C1—H1···O10ⁱⁱⁱ	1.08	2.52	3.427 (2)	141

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

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₂²⁺·Cl⁻·NO₃⁻
M_r	207.61
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	100
a, b, c (Å)	7.3695 (5), 8.2367 (5), 14.2398 (7)
V (Å³)	864.36 (8)
Z	4
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.22
Crystal size (mm)	0.27 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Photon100 CMOS detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.751, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	26823, 812, 812
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.053, 0.80
No. of reflections	812
No. of parameters	66
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.26

Computer programs: COLLECT (Bruker, 2004), SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), MoPro (Jelsch et al., 2005), DIAMOND (Brandenburg, 1998), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H34···O10	1.033 (4)	2.41 (1)	2.896 (2)	107.4 (9)
N3—H34···N1	1.033 (4)	2.429 (9)	3.263 (2)	137.1 (8)
N3—H31···Cl1ⁱ	1.033 (4)	2.181 (4)	3.179 (2)	161.8 (5)
N3—H32···Cl1	1.033 (4)	2.183 (5)	3.156 (2)	156.2 (5)
C2—H2···O11	1.08	2.48	3.299 (2)	132
C1—H1···O10ⁱⁱ	1.08	2.52	3.427 (2)	141

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

Acknowledgements

We thank the Secretary of State for Scientific Research and Technology of Tunisia for financial support.

References

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