Ethane-1,2-diaminium dipicrate dihydrate

Jerry P Jasinski; Ray J Butcher; Q N M Hakim Al-arique; H S Yathirajan; B Narayana

doi:10.1107/S1600536811004855

. 2011 Feb 16;67(Pt 3):o637–o638. doi: 10.1107/S1600536811004855

Ethane-1,2-diaminium dipicrate dihydrate

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, Q N M Hakim Al-arique ^c, H S Yathirajan ^c, B Narayana ^d

PMCID: PMC3052063 PMID: 21522391

Abstract

The title compound, C₂H₁₀N₂ ²⁺·2C₆H₂N₃O₇ ⁻·2H₂O, crystallizes with a complete picrate anion and half an ethylenediammonium dication on a mirror plane, and two half-water molecules (both on a mirror plane) in the asymmetric unit. The N atoms from separate half ethylenediammonium dications are in near proximity to a phenolate O atom and two o-NO₂ groups from the picrate anion, which, along with the water molecule form N—H⋯O, O—H⋯O and weak intermolecular C—H⋯O hydrogen bonds that create cyclic patterns with graph-set descriptors R ₂ ⁴(8), R ₄ ⁴(12), and R ₄ ⁴(16). The crystal packing is strongly influenced by these intermolecular interactions between symmetry-related water molecules, the half ethylenediammonium dication and the picrate anion, forming a three-dimensional supermolecular structure.

Related literature

For related structures, see: Muthamizhchelvan et al. (2005a ▶,b ▶,c ▶); Subashini et al. (2006 ▶); Narayana et al. (2008 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For picrates of biologically important molecules, see: Harrison et al. (2007 ▶); Swamy et al. (2007 ▶).

Experimental

Crystal data

C₂H₁₀N₂ ²⁺·2C₆H₂N₃O₇ ⁻·2H₂O
M _r = 554.36
Orthorhombic,
a = 13.4795 (4) Å
b = 20.4372 (7) Å
c = 8.0410 (3) Å
V = 2215.16 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 295 K
0.52 × 0.42 × 0.27 mm

Data collection

Oxford Diffraction Gemini R diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.837, T _max = 0.960
16775 measured reflections
3846 independent reflections
2322 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.196
S = 1.03
3846 reflections
207 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); 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: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004855/om2399sup1.cif

e-67-0o637-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004855/om2399Isup2.hkl

e-67-0o637-Isup2.hkl^{(188.6KB, hkl)}

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
N4—H41⋯O2Wⁱ	0.87 (1)	2.06 (2)	2.872 (4)	156 (3)
N4—H42⋯O1	0.86 (1)	1.98 (1)	2.815 (2)	164 (2)
N4—H42⋯O7	0.86 (1)	2.41 (2)	2.9166 (16)	118 (2)
N5—H51⋯O1Wⁱⁱ	0.87 (1)	1.91 (1)	2.778 (3)	176 (3)
N5—H52⋯O1ⁱⁱⁱ	0.86 (1)	2.18 (2)	2.892 (2)	140 (2)
N5—H52⋯O2ⁱⁱⁱ	0.86 (1)	2.34 (2)	3.018 (3)	136 (2)
C3—H3⋯O6^iv	0.93	2.53	3.337 (3)	145
C7—H7⋯O2^v	0.96	2.39	3.128 (3)	134
C7—H7⋯O7^vi	0.96	2.56	3.1203 (19)	117
O1W—H1W2⋯O3	0.84 (1)	2.21 (3)	3.008 (2)	159 (6)
O1W—H1W2⋯O2	0.84 (1)	2.52 (4)	3.243 (3)	145 (5)
O2W—H2W2⋯O5	0.85 (1)	2.26 (2)	3.082 (2)	163 (7)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

QNMHA thanks the University of Mysore for use of its research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

The crystal structures of compounds similar to ethylenediammonium picrate, 3-(dimethylammonio)propanaminium dipicrate and triethylaminium picrate (Muthamizhchelvan et al., 2005a, 2005b, 2005c), 2-amino-4,6-dimethylpyrimidinium picrate (Subashini et al., 2006) and 2-aminopyrimidinium picrate (Narayana et al., 2008) have been reported. In continuation of our work on picrates of biologically important molecules (Harrison et al., 2007; Swamy et al., 2007), we have prepared a new picrate of ethylenediammonium hydrate, [C₇H₈N₄O₈] and its crystal structure is reported.

The title compound, 0.5(C₂H₁₀N₂²⁺), C₆H₂N₃O₇^-, H₂O, crystallizes with a complete picrate anion and a half-ethylenediammonium group on a mirror plane thus producing a 0.5 di-cation (i.e. protonated at both ends), and two half-water molecules (both on a mirror plane) in the asymmetric unit (Fig. 1). Bond distances and angles are in normal ranges (Allen et al., 1998). In the picrate anion the depronated phenolate oxygen atom is slightly deviated from the plane of the benzene ring (torsion angle O1/C1/C2/C3 = 177.84 (17) Å). The twist angles between the mean plane of the benzene ring and the two o-NO₂ groups are 20.3 (0)° (N1) and 39.6 (7)° (N3). The p-NO₂group is twisted by 3.3 (4)° and most likely influenced by a weak hydrogen bond interaction (O2W—H2W2···O5). The deviation of the p-NO₂ groups from the plane of the benzene ring is due to a network of hydrogen bond interactions with the half-ethylenediammonium di-cation involving both nitrogen atoms (N4 and N5 lying across a morror plane). The position of N4 and N5 from separate half-ethylenediammonium di-cations, in near proximity to a phenolate oxygen atom and two o-NO₂ groups from the picrate anion, along with the water molecule form N—H···O, O—H···O hydrogen bonds and weak C—H···O intermolecular interactions (Table 1) that create cyclic patterns with graph-set descriptors R₂⁴(8), R₄⁴(12) and R₄⁴(16). These intermolecular interactions of symmetry-related molecules link the cations and anions through a half-water molecule (on a mirror plane), the half-ethylenediammonium di-cation and the picrate anion forming a 3-D supermolecular structure (Fig. 2).

Experimental

Ethylenediamine dihydrochloride (1.33 g, 0.01 mol) was dissolved in 25 ml of water. Picric acid (2.29 g, 0.01 mol) was dissolved in 50 ml of water. Both the solutions were mixed and stirred for few minutes. The formed complex was filtered and dried. Good quality crystals were grown from ethanol solution by slow evaporation (m. p.: 476–478 K). Composition: Found (Calculated): C: 30.44 (30.40); H: 2.92 (2.96); N: 20.29% (20.36%).